JP6612410B2 - Ion exchange membrane - Google Patents

Ion exchange membrane Download PDF

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JP6612410B2
JP6612410B2 JP2018176906A JP2018176906A JP6612410B2 JP 6612410 B2 JP6612410 B2 JP 6612410B2 JP 2018176906 A JP2018176906 A JP 2018176906A JP 2018176906 A JP2018176906 A JP 2018176906A JP 6612410 B2 JP6612410 B2 JP 6612410B2
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layer
ion exchange
electrolysis
exchange membrane
ion
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JP2019007021A (en
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篤 中島
直紀 坂本
卓也 森川
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Asahi Kasei Corp
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
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Description

本発明は、イオン交換膜に関する。   The present invention relates to an ion exchange membrane.

含フッ素イオン交換膜は、耐熱性や耐薬品性などが優れており、塩化アルカリ電解用、オゾン発生電解用、燃料電池用、水電解用、塩酸電解用などの電解用隔膜として、種々の用途に用いられている。   Fluorine ion exchange membranes have excellent heat resistance and chemical resistance, and are used in various applications as diaphragms for electrolysis such as alkaline chloride electrolysis, ozone generation electrolysis, fuel cells, water electrolysis, and hydrochloric acid electrolysis. It is used for.

これらの中で、特に、塩素と水酸化アルカリを製造する塩化アルカリの電解では、近年、イオン交換膜法が主流となっている。塩化アルカリの電解に用いられるイオン交換膜には、様々な性能が求められている。例えば、高い電流効率及び低い電解電圧で電解を行えること、製造した水酸化アルカリ中に含まれる不純物（特に塩化アルカリ等）の濃度が低いこと等の電解性能、及び、膜強度が高く、膜の取扱い時や電解時に損傷しない等の膜強度などの性能が要求されている。そして、イオン交換膜の電解性能と膜強度とはトレードオフの関係にあるが、両者が高いイオン交換膜の開発が求められている。   Among these, particularly in the electrolysis of alkali chloride for producing chlorine and alkali hydroxide, the ion exchange membrane method has become the mainstream in recent years. Various performances are required for ion exchange membranes used for alkali chloride electrolysis. For example, it is possible to perform electrolysis with high current efficiency and low electrolysis voltage, electrolysis performance such as low concentration of impurities (especially alkali chloride, etc.) contained in the manufactured alkali hydroxide, and high film strength. There is a demand for performance such as film strength that does not cause damage during handling or electrolysis. The electrolytic performance of the ion exchange membrane and the membrane strength are in a trade-off relationship, but the development of an ion exchange membrane having a high both is required.

特許文献１には、スルホン酸基を有する含フッ素重合体層と、カルボン酸基を有する含フッ素重合体層の少なくとも二層から成るイオン交換膜が開示されている。   Patent Document 1 discloses an ion exchange membrane comprising at least two layers of a fluorine-containing polymer layer having a sulfonic acid group and a fluorine-containing polymer layer having a carboxylic acid group.

特開２００１−３２３０８４号公報JP 2001-323084 A

しかしながら、特許文献１に記載のイオン交換膜は、膜強度と電解性能との両立において更なる改善の余地がある。
本発明は、上述した従来技術が有する課題に鑑みてなされたものであり、膜強度と電解性能の両方に優れるイオン交換膜を提供することを目的とする。 However, the ion exchange membrane described in Patent Document 1 has room for further improvement in achieving both membrane strength and electrolytic performance.
This invention is made | formed in view of the subject which the prior art mentioned above has, and aims at providing the ion exchange membrane which is excellent in both membrane strength and electrolysis performance.

本発明者らは、上記課題を解決するため鋭意検討を行った結果、イオン交換膜内に存在するイオンクラスターを電解中に収縮させ、イオン交換膜の電解後のイオンクラスター径が、電解前のイオンクラスター径に対して所定の割合で小さくなるように制御することにより、電解性能が飛躍的に向上することを見出し、本発明を成すに至った。
すなわち、本発明は、以下のとおりである。
［１］
スルホン酸基を有する含フッ素重合体を含む層Ａと、
カルボン酸基を有する含フッ素重合体を含む層Ｂと、
を有し、
下記電解条件における電解前の前記層Ｂのイオンクラスター径に対する、前記電解後の前記層Ｂのイオンクラスター径の割合〔（前記電解後の層Ｂのイオンクラスター径）／（前記電解前の層Ｂのイオンクラスター径）〕が０．８３〜０．９５である、イオン交換膜：
（電解条件）
３．５規定（Ｎ）の塩化ナトリウム水溶液が供給された陽極室と、１０．８規定（Ｎ）の水酸化ナトリウム水溶液が供給された陰極室との間に前記イオン交換膜が配置されたゼロギャップ電解槽において、温度が８５℃、電流密度が６ｋＡ／ｍ2の条件で７日間電解を行う。
［２］
前記電解前の層Ｂのイオンクラスター径が２．５〜４．０ｎｍであり、
前記電解後の層Ｂのイオンクラスター径が２．０〜３．３ｎｍである、［１］に記載のイオン交換膜。
［３］
前記電解前における、前記層Ａの厚みと前記層Ｂの厚みとの合計が５５μｍ以上である、［１］又は［２］に記載のイオン交換膜。
［４］
前記電解前の層Ａのイオンクラスター径が３．０〜４．５ｎｍである、［１］〜［３］のいずれかに記載のイオン交換膜。
［５］
前記電解前の層Ａの厚さが５０〜１８０μｍであり、
前記電解前の層Ｂの厚さが５〜２０μｍである、［１］〜［４］のいずれかに記載のイオン交換膜。
［６］
前記層Ａは、下記式（２）で表される化合物の重合体を含み、
前記層Ｂは下記式（３）で表される化合物の重合体を含む、［１］〜［５］のいずれかに記載のイオン交換膜：
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）a−Ｏ−（ＣＦ2）b−ＳＯ2Ｆ （２）
（式（２）中、ａは０〜２の整数、ｂは１〜４の整数、Ｙは−Ｆ又は−ＣＦ3を表す。）
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）c−Ｏ−（ＣＦ2）d−ＣＯＯＲ （３）
（式（３）中、ｃは０〜２の整数、ｄは１〜４の整数、Ｙは−Ｆ又は−ＣＦ3、Ｒは−ＣＨ3、−Ｃ2Ｈ5、又は−Ｃ3Ｈ7を表す。）
［７］
［１］〜［６］のいずれかに記載のイオン交換膜を備える、電解槽。 As a result of intensive studies to solve the above problems, the present inventors have contracted ion clusters present in the ion exchange membrane during electrolysis, and the ion cluster diameter after electrolysis of the ion exchange membrane is the same as before electrolysis. It has been found that the electrolytic performance is dramatically improved by controlling the ion cluster diameter so as to decrease at a predetermined ratio, and the present invention has been achieved.
That is, the present invention is as follows.
[1]
A layer A containing a fluoropolymer having a sulfonic acid group;
A layer B containing a fluoropolymer having a carboxylic acid group;
Have
Ratio of ion cluster diameter of layer B after electrolysis to the ion cluster diameter of layer B before electrolysis under the following electrolysis conditions [(ion cluster diameter of layer B after electrolysis) / (layer B before electrolysis] The ion cluster diameter)]] is 0.83 to 0.95:
(Electrolytic conditions)
Zero in which the ion exchange membrane is disposed between an anode chamber supplied with a 3.5 N (N) sodium chloride aqueous solution and a cathode chamber supplied with a 10.8 N (N) sodium hydroxide aqueous solution In the gap electrolytic cell, electrolysis is performed for 7 days under the conditions of a temperature of 85 ° C. and a current density of 6 kA / m 2 .
[2]
The ion cluster diameter of the layer B before electrolysis is 2.5 to 4.0 nm,
The ion exchange membrane according to [1], wherein the ion cluster diameter of the layer B after electrolysis is 2.0 to 3.3 nm.
[3]
The ion exchange membrane according to [1] or [2], wherein the total of the thickness of the layer A and the thickness of the layer B is 55 μm or more before the electrolysis.
[4]
The ion exchange membrane according to any one of [1] to [3], wherein the ion cluster diameter of the layer A before electrolysis is 3.0 to 4.5 nm.
[5]
The thickness of the layer A before electrolysis is 50 to 180 μm,
The ion exchange membrane according to any one of [1] to [4], wherein the thickness of the layer B before electrolysis is 5 to 20 μm.
[6]
The layer A includes a polymer of a compound represented by the following formula (2),
The ion exchange membrane according to any one of [1] to [5], wherein the layer B includes a polymer of a compound represented by the following formula (3):
CF 2 = CF- (OCF 2 CYF ) a -O- (CF 2) b -SO 2 F (2)
(In Formula (2), a represents an integer of 0 to 2, b represents an integer of 1 to 4, and Y represents —F or —CF 3. )
CF 2 = CF- (OCF 2 CYF ) c -O- (CF 2) d -COOR (3)
(In the formula (3), c is an integer of 0 to 2, d is an integer from 1 to 4, Y is -F or -CF 3, R is -CH 3, -C 2 H 5, or -C 3 H 7 Represents.)
[7]
An electrolytic cell comprising the ion exchange membrane according to any one of [1] to [6].

本発明のイオン交換膜は、膜強度及び電解性能に優れる。   The ion exchange membrane of the present invention is excellent in membrane strength and electrolytic performance.

本実施形態のイオン交換膜の一例の概略断面図である。It is a schematic sectional drawing of an example of the ion exchange membrane of this embodiment. 本実施形態の電解槽の一例の模式図である。It is a schematic diagram of an example of the electrolytic cell of this embodiment.

以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明する。なお、本発明は、以下の本実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。   Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

本実施形態のイオン交換膜は、スルホン酸基を有する含フッ素重合体を含む層Ａ（以下、単に「層Ａ」と記載することもある）とカルボン酸基を有する含フッ素重合体を含む層Ｂ（以下、単に「層Ｂ」と記載することもある）を有し、下記電解条件（１）における電解前の前記層Ｂのイオンクラスター径に対する、前記電解後の前記層Ｂのイオンクラスター径の割合〔（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）〕が０．８３〜０．９５である。ここで、電解条件（１）は、３．５規定（Ｎ）の塩化ナトリウム水溶液が供給された陽極室と、１０．８規定（Ｎ）の水酸化ナトリウム水溶液が供給された陰極室との間にイオン交換膜が配置されたゼロギャップ電解槽において、温度が８５℃、電流密度が６ｋＡ／ｍ2の条件で７日間電解を行うこととする。このように構成されているため、本実施形態のイオン交換膜は、膜強度及び電解性能に優れる。以下、上記の電解条件（１）による電解を単に「電解」ともいう。なお、本明細書において、「ゼロギャップ」とは、電解層中、イオン交換膜が陰極及び陽極の双方と接した状態（イオン交換膜と陽極との間の距離、及びイオン交換膜と陰極との間の距離がゼロの状態）を意味し、これらの部材は電極（陽極又は陰極）の表面全体でイオン交換膜と接している状態であってもよいし、電極表面のある点においてイオン交換膜と接している状態であってもよい。 The ion exchange membrane of this embodiment includes a layer A containing a fluorinated polymer having a sulfonic acid group (hereinafter sometimes simply referred to as “layer A”) and a layer containing a fluorinated polymer having a carboxylic acid group. B (hereinafter sometimes simply referred to as “layer B”), and the ion cluster diameter of the layer B after the electrolysis relative to the ion cluster diameter of the layer B before the electrolysis under the following electrolysis conditions (1) The ratio [(ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis)] is 0.83 to 0.95. Here, the electrolysis condition (1) is between the anode chamber supplied with the 3.5 N (N) sodium chloride aqueous solution and the cathode chamber supplied with the 10.8 N (N) sodium hydroxide aqueous solution. In a zero-gap electrolytic cell in which an ion exchange membrane is disposed, electrolysis is performed for 7 days under conditions of a temperature of 85 ° C. and a current density of 6 kA / m 2 . Since it is constituted in this way, the ion exchange membrane of this embodiment is excellent in membrane strength and electrolysis performance. Hereinafter, the electrolysis under the above electrolysis condition (1) is also simply referred to as “electrolysis”. In the present specification, “zero gap” means that the ion exchange membrane is in contact with both the cathode and the anode in the electrolytic layer (the distance between the ion exchange membrane and the anode, and the ion exchange membrane and the cathode These members may be in contact with the ion exchange membrane over the entire surface of the electrode (anode or cathode) or at some point on the electrode surface. It may be in contact with the film.

図１に本実施形態のイオン交換膜の構成の一例の概略断面図を示す。本実施形態のイオン交換膜は、スルホン酸基を有する含フッ素重合体を含む層Ａ（４）と、カルボン酸基を有する含フッ素重合体を含む層Ｂ（５）とが積層され、膜内部に強化芯材３と連通孔２ａ及び２ｂを有している。通常、スルホン酸基を有する含フッ素重合体を含む層Ａ（４）が電解層の陽極側（α）に、カルボン酸基を有する含フッ素重合体を含む層Ｂ（５）が電解層の陰極側（β）になるように設置される。また、膜表面には、コーティング層６及び７を有している。図１において、連通孔２ａ及び強化芯材３は、紙面に対して垂直方向に形成され、連通孔２ｂは、紙面の上下方向に形成されている。即ち、紙面の上下方向に形成された連通孔２ｂは、強化芯材３に対して略垂直方向に沿って形成されている。また、連通孔２ａ及び２ｂは、層Ａの陽極側表面に面している箇所８を有していても構わない。図１に示すように、本実施形態のイオン交換膜は、層Ａの表面と層Ｂの表面とが接するように積層されていることが好ましい。以下、層Ａと層Ｂを合わせて膜本体と称することがある。   FIG. 1 shows a schematic cross-sectional view of an example of the configuration of the ion exchange membrane of the present embodiment. In the ion exchange membrane of this embodiment, a layer A (4) containing a fluorinated polymer having a sulfonic acid group and a layer B (5) containing a fluorinated polymer having a carboxylic acid group are laminated, Are provided with a reinforcing core 3 and communication holes 2a and 2b. Usually, the layer A (4) containing a fluorinated polymer having a sulfonic acid group is on the anode side (α) of the electrolytic layer, and the layer B (5) containing a fluorinated polymer having a carboxylic acid group is the cathode of the electrolytic layer. Installed to be on the side (β). Moreover, it has the coating layers 6 and 7 on the film | membrane surface. In FIG. 1, the communication hole 2a and the reinforcing core 3 are formed in a direction perpendicular to the paper surface, and the communication hole 2b is formed in the vertical direction of the paper surface. That is, the communication hole 2 b formed in the vertical direction of the paper surface is formed along a substantially vertical direction with respect to the reinforcing core material 3. Further, the communication holes 2a and 2b may have a portion 8 facing the anode side surface of the layer A. As shown in FIG. 1, the ion exchange membrane of this embodiment is preferably laminated so that the surface of the layer A and the surface of the layer B are in contact with each other. Hereinafter, the layer A and the layer B may be collectively referred to as a film body.

〔層Ａ〕
本実施形態のイオン交換膜に含まれる層Ａは、スルホン酸基を有する含フッ素重合体Ａ（以下、単に「重合体Ａ」と記載することもある。）を含み、重合体Ａからなることが好ましい。ここで、「スルホン酸基を有する含フッ素重合体」とは、スルホン酸基、又は、加水分解によりスルホン酸基となり得るスルホン酸基前駆体を有する含フッ素重合体のことをいう。なお、層Ａには重合体Ａの他に後述する重合体Ｂを層Ａ１００質量％に対して２０質量％未満の範囲で含んでいてもよく、層Ａ１００質量％に対して重合体Ａを８０質量％以上含むことが好ましい。 [Layer A]
The layer A included in the ion exchange membrane of the present embodiment includes a fluorinated polymer A having a sulfonic acid group (hereinafter sometimes simply referred to as “polymer A”), and is made of the polymer A. Is preferred. Here, the “fluorinated polymer having a sulfonic acid group” means a fluorinated polymer having a sulfonic acid group or a sulfonic acid group precursor that can be converted into a sulfonic acid group by hydrolysis. In addition to the polymer A, the layer A may contain a polymer B, which will be described later, in a range of less than 20% by mass with respect to 100% by mass of the layer A. It is preferable to contain at least mass%.

層Ａを構成する、スルホン酸基を有する含フッ素重合体Ａは、例えば、以下の第１群の単量体と第２群の単量体とを共重合する、又は第２群の単量体を単独重合することによって製造することができる。重合体Ａが共重合体の場合は、ブロック重合体であってもランダム重合体であってもよい。   The fluorine-containing polymer A having a sulfonic acid group constituting the layer A is, for example, copolymerized with the following first group of monomers and second group of monomers, or the second group of monomers: It can be produced by homopolymerizing the body. When the polymer A is a copolymer, it may be a block polymer or a random polymer.

第１群の単量体としては、特に限定されないが、例えば、フッ化ビニル化合物が挙げられる。
フッ化ビニル化合物としては、下記一般式（１）で表わされるものが好ましい。
ＣＦ2＝ＣＸ1Ｘ2 （１）
（一般式（１）において、Ｘ1及びＸ2は、それぞれ独立に、−Ｆ、−Ｃｌ、−Ｈ、又は−ＣＦ3を表す。） Although it does not specifically limit as a 1st group monomer, For example, a vinyl fluoride compound is mentioned.
As a vinyl fluoride compound, what is represented by following General formula (1) is preferable.
CF 2 = CX 1 X 2 (1)
(In the general formula (1), X 1 and X 2 each independently represent —F, —Cl, —H, or —CF 3. )

上記一般式（１）で表わされるフッ化ビニル化合物としては、特に限定されないが、例えば、フッ化ビニル、テトラフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン等が挙げられる。   The vinyl fluoride compound represented by the general formula (1) is not particularly limited, and examples thereof include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene. It is done.

特に、本実施形態に係るイオン交換膜をアルカリ電解用膜として用いる場合、フッ化ビニル化合物は、パーフルオロ単量体であることが好ましく、テトラフルオロエチレン、ヘキサフルオロプロピレンからなる群より選ばれるパーフルオロ単量体がより好ましく、テトラフルオロエチレン（ＴＦＥ）がさらに好ましい。   In particular, when the ion exchange membrane according to this embodiment is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoromonomer, and is selected from the group consisting of tetrafluoroethylene and hexafluoropropylene. A fluoromonomer is more preferable, and tetrafluoroethylene (TFE) is more preferable.

第１群の単量体は一種を単独で用いてもよいし、二種以上を併用してもよい。   The first group of monomers may be used alone or in combination of two or more.

第２群の単量体としては、特に限定されないが、例えば、スルホン酸型イオン交換基に変換し得る官能基を有するビニル化合物が挙げられる。   Although it does not specifically limit as a monomer of 2nd group, For example, the vinyl compound which has a functional group which can be converted into a sulfonic acid type ion exchange group is mentioned.

スルホン酸型イオン交換基に変換し得る官能基を有するビニル化合物としては、下記一般式（２）で表わされるものが好ましい。
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）a−Ｏ−（ＣＦ2）b−ＳＯ2Ｆ （２）
（式（２）中、ａは０〜２の整数、ｂは１〜４の整数、Ｙは−Ｆ又は−ＣＦ3を表す。）
式（２）において、ａが２のとき、複数存在するＹは互いに独立である。 As the vinyl compound having a functional group that can be converted into a sulfonic acid type ion exchange group, those represented by the following general formula (2) are preferable.
CF 2 = CF- (OCF 2 CYF ) a -O- (CF 2) b -SO 2 F (2)
(In Formula (2), a represents an integer of 0 to 2, b represents an integer of 1 to 4, and Y represents —F or —CF 3. )
In Formula (2), when a is 2, a plurality of Ys are independent of each other.

第２群の単量体としては、特に限定されないが、例えば、下記に表す単量体等が挙げられる：
ＣＦ2＝ＣＦＯＣＦ2ＣＦ2ＳＯ2Ｆ、
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＳＯ2Ｆ、
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＣＦ2ＳＯ2Ｆ、
ＣＦ2＝ＣＦ（ＣＦ2）2ＳＯ2Ｆ、
ＣＦ2＝ＣＦＯ〔ＣＦ2ＣＦ（ＣＦ3）Ｏ〕2ＣＦ2ＣＦ2ＳＯ2Ｆ、
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ2ＯＣＦ3）ＯＣＦ2ＣＦ2ＳＯ2Ｆ。 Although it does not specifically limit as a monomer of 2nd group, For example, the monomer etc. which are shown below are mentioned:
CF 2 = CFOCF 2 CF 2 SO 2 F,
CF 2 = CFOCF 2 CF (CF 3 ) OCF 2 CF 2 SO 2 F,
CF 2 = CFOCF 2 CF (CF 3 ) OCF 2 CF 2 CF 2 SO 2 F,
CF 2 = CF (CF 2 ) 2 SO 2 F,
CF 2 = CFO [CF 2 CF (CF 3 ) O] 2 CF 2 CF 2 SO 2 F,
CF 2 = CFOCF 2 CF (CF 2 OCF 3) OCF 2 CF 2 SO 2 F.

これらの中でも、ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＣＦ2ＳＯ2Ｆ、及びＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＳＯ2Ｆが好ましい。 Among them, CF 2 = CFOCF 2 CF ( CF 3) OCF 2 CF 2 CF 2 SO 2 F, and CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 SO 2 F are preferred.

第２群の単量体は一種を単独で使用してもよいし、二種以上を併用してもよい。   The second group of monomers may be used alone or in combination of two or more.

重合体Ａを構成する単量体の組み合わせの種類、その比率及び重合度等は、特に限定されない。また、層Ａ中に含まれる重合体Ａは、一種単独であっても二種以上の組み合わせであってもよい。また、スルホン酸基を有する含フッ素重合体Ａのイオン交換容量は、上記一般式（１）と（２）で表される単量体の比を変えることにより調整することができる。   There are no particular restrictions on the type of monomer combination constituting the polymer A, its ratio, the degree of polymerization, and the like. Further, the polymer A contained in the layer A may be a single type or a combination of two or more types. The ion exchange capacity of the fluorinated polymer A having a sulfonic acid group can be adjusted by changing the ratio of the monomers represented by the general formulas (1) and (2).

層Ａは、構成する重合体Ａの組成により、単層であってもよいし、２層以上から構成されていてもよい。   The layer A may be a single layer or may be composed of two or more layers, depending on the composition of the polymer A constituting the layer A.

層Ａが単層である場合、その厚みは５０μｍ以上１８０μｍ以下が好ましく、８０μｍ以上１６０μｍ以下がより好ましい。層Ａの厚みが該範囲内にあると、膜本体の強度がより高くなる傾向にある。   When the layer A is a single layer, the thickness is preferably 50 μm or more and 180 μm or less, and more preferably 80 μm or more and 160 μm or less. When the thickness of the layer A is within this range, the strength of the membrane body tends to be higher.

本明細書において、層Ａが２層構造の場合、陽極に接する側の層を層Ａ−１とし、層Ｂと接する側の層を含フッ素重合体層Ａ−２とする。ここで、層Ａ−１を形成する含フッ素重合体（「含フッ素重合体Ａ−１」とも称する）と、層Ａ−２を形成する含フッ素重合体（「含フッ素重合体Ａ−２」とも称する）とは、組成が異なるものとすることが好ましい。層Ａ−１の厚みは１０μｍ以上６０μｍ以下が好ましい。層Ａ−２の厚みは３０μｍ以上１２０μｍ以下が好ましく、４０μｍ以上１００μｍ以下がより好ましい。層Ａ−１及び層Ａ−２の厚みが上記範囲内にあると、膜本体の強度を十分に保つことができる。また、層Ａ−１及び層Ａ−２の厚みの合計は、５０μｍ以上１８０μｍ以下が好ましく、８０μｍ以上１６０μｍ以下がより好ましい。層Ａが２層以上から構成される場合は、組成の異なる重合体Ａから構成される２枚以上のフィルムを積層して層Ａを形成させてもよい。   In this specification, when layer A has a two-layer structure, the layer in contact with the anode is referred to as layer A-1, and the layer in contact with layer B is referred to as fluoropolymer layer A-2. Here, the fluorinated polymer forming the layer A-1 (also referred to as “fluorinated polymer A-1”) and the fluorinated polymer forming the layer A-2 (“fluorinated polymer A-2”). The composition is preferably different from that of the other. The thickness of the layer A-1 is preferably 10 μm or more and 60 μm or less. The thickness of the layer A-2 is preferably 30 μm or more and 120 μm or less, and more preferably 40 μm or more and 100 μm or less. When the thicknesses of the layer A-1 and the layer A-2 are within the above range, the strength of the film main body can be sufficiently maintained. The total thickness of the layer A-1 and the layer A-2 is preferably 50 μm or more and 180 μm or less, and more preferably 80 μm or more and 160 μm or less. When the layer A is composed of two or more layers, the layer A may be formed by laminating two or more films composed of polymers A having different compositions.

〔層Ｂ〕
本実施形態のイオン交換膜に含まれる層Ｂは、カルボン酸基を有する含フッ素重合体Ｂ（以下、単に「重合体Ｂ」と記載することもある。）を含む。ここで、「カルボン酸基を有する含フッ素重合体」とは、カルボン酸基、又は、加水分解によりカルボン酸基となり得るカルボン酸基前駆体を有する含フッ素重合体のことをいう。なお、層Ｂには重合体Ｂ以外の成分を層Ｂ１００質量％に対して１０質量％未満の範囲で含んでいてもよく、層Ｂ１００質量％に対して重合体Ｂを９０質量％以上含むことが好ましく、重合体Ｂを１００質量％含むことがとりわけ好ましい。なお、層Ｂにおいて重合体Ｂ以外に含まれていてもよい成分としては、以下に限定されないが、例えば、塩化カリウムのような金属塩化物等が挙げられる。 [Layer B]
The layer B included in the ion exchange membrane of the present embodiment includes a fluorinated polymer B having a carboxylic acid group (hereinafter sometimes simply referred to as “polymer B”). Here, the “fluorinated polymer having a carboxylic acid group” refers to a fluorinated polymer having a carboxylic acid group or a carboxylic acid group precursor that can be converted into a carboxylic acid group by hydrolysis. The layer B may contain a component other than the polymer B in a range of less than 10% by mass with respect to 100% by mass of the layer B, and 90% by mass or more of the polymer B with respect to 100% by mass of the layer B. It is particularly preferable that 100% by mass of the polymer B is contained. In addition, as a component which may be contained other than the polymer B in the layer B, although not limited to the following, For example, metal chlorides, such as potassium chloride, etc. are mentioned.

層Ｂを構成するカルボン酸基を有する含フッ素系重合体は、例えば、上記第１群の単量体と以下の第３群の単量体とを共重合する、又は第３群の単量体を単独重合することによって製造することができる。重合体Ｂが共重合体の場合、ブロック共重合体であってもランダム重合体であってもよい。   The fluorine-containing polymer having a carboxylic acid group constituting the layer B is, for example, a copolymer of the first group of monomers and the following third group of monomers, or the third group of monomers. It can be produced by homopolymerizing the body. When the polymer B is a copolymer, it may be a block copolymer or a random polymer.

第３群の単量体としては、特に限定されないが、例えば、カルボン酸型イオン交換基に変換し得る官能基を有するビニル化合物が挙げられる。   Although it does not specifically limit as a monomer of 3rd group, For example, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group is mentioned.

カルボン酸型イオン交換基に変換し得る官能基を有するビニル化合物としては、下記一般式（３）で表されるものが好ましい。
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）c−Ｏ−（ＣＦ2）d−ＣＯＯＲ （３）
（一般式（３）中、ｃは０〜２の整数、ｄは１〜４の整数を表し、Ｙは−Ｆ又は−ＣＦ3、Ｒは−ＣＨ3、−Ｃ2Ｈ5、又は−Ｃ3Ｈ7を表す。）
一般式（３）において、ｃが２のとき、複数存在するＹは互いに独立である。上記一般式（３）において、Ｙが−ＣＦ3であり、Ｒが−ＣＨ3であることが好ましい。 As the vinyl compound having a functional group that can be converted into a carboxylic acid ion exchange group, those represented by the following general formula (3) are preferable.
CF 2 = CF- (OCF 2 CYF ) c -O- (CF 2) d -COOR (3)
(In General Formula (3), c represents an integer of 0 to 2, d represents an integer of 1 to 4, Y represents —F or —CF 3 , R represents —CH 3 , —C 2 H 5 , or —C. 3 represents H 7 )
In the general formula (3), when c is 2, a plurality of Ys are independent of each other. In the general formula (3), Y is preferably —CF 3 and R is preferably —CH 3 .

特に、本実施形態のイオン交換膜をアルカリ電解用イオン交換膜として用いる場合、第３群の単量体としてパーフルオロ単量体を少なくとも用いることが好ましい。ただし、エステル基中のアルキル基（上記Ｒ参照）は加水分解される時点で重合体から失われるため、アルキル基（Ｒ）はパーフルオロアルキル基でなくてもよい。これらの中でも、第３群の単量体として、特に限定されないが、例えば、下記に表す単量体がより好ましい：
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＯＯＣＨ3、
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）2ＣＯＯＣＨ3、
ＣＦ2＝ＣＦ［ＯＣＦ2ＣＦ（ＣＦ3）］2Ｏ（ＣＦ2）2ＣＯＯＣＨ3、
ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＣＯＯＣＨ3、
ＣＦ2＝ＣＦＯ（ＣＦ2）2ＣＯＯＣＨ3、
ＣＦ2＝ＣＦＯ（ＣＦ2）3ＣＯＯＣＨ3。 In particular, when the ion exchange membrane of this embodiment is used as an ion exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoromonomer as the third group of monomers. However, since the alkyl group (see R above) in the ester group is lost from the polymer at the time of hydrolysis, the alkyl group (R) may not be a perfluoroalkyl group. Among these, the monomer of the third group is not particularly limited, but for example, the monomers shown below are more preferable:
CF 2 = CFOCF 2 CF (CF 3 ) OCF 2 COOCH 3 ,
CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 COOCH 3 ,
CF 2 = CF [OCF 2 CF (CF 3)] 2 O (CF 2) 2 COOCH 3,
CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 COOCH 3 ,
CF 2 = CFO (CF 2 ) 2 COOCH 3 ,
CF 2 = CFO (CF 2) 3 COOCH 3.

第３群の単量体は一種を単独で使用してもよいし、二種以上を併用してもよい。
重合体Ｂを構成する単量体の組み合わせの種類、その比率及び重合度等は、特に限定されない。また、層Ｂ中に含まれる重合体Ｂは、一種単独であっても二種以上の組み合わせであってもよい。また、カルボン酸基を有する含フッ素重合体Ｂのイオン交換容量は、上記一般式（３）と（４）で表される単量体の比を変えることにより調整することができる。 The third group of monomers may be used alone or in combination of two or more.
There are no particular limitations on the type of combination of the monomers constituting the polymer B, the ratio thereof, the degree of polymerization, and the like. Further, the polymer B contained in the layer B may be a single type or a combination of two or more types. The ion exchange capacity of the fluoropolymer B having a carboxylic acid group can be adjusted by changing the ratio of the monomers represented by the general formulas (3) and (4).

層Ｂの厚みとしては、５μｍ以上５０μｍ以下が好ましく、より好ましくは５μｍ以上２０μｍ以下である。層Ｂの厚みがこの範囲内にあると、イオン交換膜の電解性能がより向上する傾向にあり、結果としてより高い電流効率及び低い電圧を達成できる傾向にある。また、層Ｂの膜厚みが上記の範囲内にあると、電解中に層Ｂのクラスターが収縮しやすく、〔（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）〕の値が小さくなりやすい。   The thickness of the layer B is preferably 5 μm or more and 50 μm or less, more preferably 5 μm or more and 20 μm or less. When the thickness of the layer B is within this range, the electrolytic performance of the ion exchange membrane tends to be further improved, and as a result, higher current efficiency and lower voltage tend to be achieved. In addition, when the film thickness of the layer B is within the above range, the cluster of the layer B easily contracts during electrolysis, [(ion cluster diameter of the layer B after electrolysis) / (ion cluster of the layer B before electrolysis). The value of (diameter)] tends to be small.

本実施形態のイオン交換膜において、電解性能と強度をより向上させる観点から、層Ａは、上記式（２）で表される化合物の重合体を含み、かつ、層Ｂは上記式（３）で表される化合物の重合体を含むことが好ましい。   In the ion exchange membrane of the present embodiment, from the viewpoint of further improving electrolysis performance and strength, the layer A contains a polymer of the compound represented by the above formula (2), and the layer B has the above formula (3). It is preferable that the polymer of the compound represented by these is included.

本実施形態のイオン交換膜において、電解前の、層Ａの厚みと前記層Ｂの厚みの合計が５５μｍ以上であることが好ましく、５５μｍ以上２１０μｍ以下であることがより好ましく、８５μｍ以上１９０μｍ以下であることがさらに好ましい。層Ａと層Ｂの厚みの合計が、該範囲内にあることにより、膜本体の強度がより向上する傾向にある。同様の観点から、電解前の層Ａの厚さが５０〜１８０μｍであり、かつ、電解前の層Ｂの厚さが５〜３０μｍであることが好ましい。ここで、層Ａ及び層Ｂのそれぞれの厚みは、後述する加水分解工程を経た後であって、前述した電解を行う前のイオン交換膜を構成する層Ａ及び層Ｂのそれぞれの厚みを意味するものとし、実施例に記載の方法で測定することができる。また、上記厚みは、例えば、後述するフィルム化工程の押し出し量、及びフィルムの引き取り速度を調節することで制御することができる。   In the ion exchange membrane of the present embodiment, the total thickness of layer A and layer B before electrolysis is preferably 55 μm or more, more preferably 55 μm or more and 210 μm or less, and 85 μm or more and 190 μm or less. More preferably it is. When the total thickness of the layer A and the layer B is within the range, the strength of the film main body tends to be further improved. From the same viewpoint, the thickness of the layer A before electrolysis is preferably 50 to 180 μm, and the thickness of the layer B before electrolysis is preferably 5 to 30 μm. Here, each thickness of the layer A and the layer B means the thickness of each of the layer A and the layer B constituting the ion exchange membrane after the hydrolysis process described later and before performing the above-described electrolysis. It can be measured by the method described in the examples. Moreover, the said thickness can be controlled by adjusting the extrusion amount of the film forming process mentioned later, and the take-up speed of a film, for example.

〔電解前後のイオンクラスター径の比〕
本実施形態のイオン交換膜は、含水状態においてイオンクラスターが存在する。イオンクラスターとは、イオンが通る空間のことであり、イオン交換基の会合によって形成される。イオンクラスター径はイオン交換基の会合度合いや膜本体の含水率によって変化し、含フッ素重合体のイオン交換容量や加水分解の条件によって制御でき、さらに、通電によりクラスター径が変化する場合がある。本実施形態のイオン交換膜は、電解前後のイオンクラスター径の比が所定の範囲内にあることにより、イオン交換膜の膜強度と電解性能の両方に優れる。 [Ratio of ion cluster diameter before and after electrolysis]
In the ion exchange membrane of this embodiment, ion clusters exist in a water-containing state. An ion cluster is a space through which ions pass and is formed by association of ion exchange groups. The ion cluster diameter varies depending on the degree of association of the ion exchange groups and the moisture content of the membrane body, and can be controlled by the ion exchange capacity of the fluoropolymer and the hydrolysis conditions. Further, the cluster diameter may change due to current application. The ion exchange membrane of the present embodiment is excellent in both membrane strength and electrolysis performance of the ion exchange membrane because the ratio of ion cluster diameters before and after electrolysis is within a predetermined range.

本実施形態のイオン交換膜は、電解条件（１）で電解を行うと、〔（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）〕が０．８３〜０．９５となり、好ましくは０．８３〜０．９２であり、より好ましくは０．８３〜０．９０である。ここで、電解条件（１）は、陽極室と陰極室との間に該イオン交換膜が配置され、前記陽極室に３．５規定（Ｎ）の塩化ナトリウム水溶液が供給され、前記陰極室に１０．８規定（Ｎ）の水酸化ナトリウム水溶液が供給され、電解温度が８５℃、電流密度が６ｋＡ／ｍ2の条件で７日間電解を行うことである。ここで、「電解前の層Ｂのイオンクラスター径」とは、後述するイオン交換膜の製造における加水分解工程後であり、かつ、電解に用いる前のイオン交換膜中の層Ｂのイオンクラスター径のことをいう。「電解後の層Ｂのイオンクラスター径」とは、上記電解条件（１）で電解を行った後のイオン交換膜中の、層Ｂのイオンクラスター径のことをいう。なお、本明細書中、〔（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）〕のことを、単に「電解前後の層Ｂのイオンクラスター径の比」と記載することもある。 When the ion exchange membrane of this embodiment is electrolyzed under electrolysis conditions (1), [(ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis)] is 0.83. 0.95, preferably 0.83 to 0.92, and more preferably 0.83 to 0.90. Here, the electrolysis condition (1) is that the ion exchange membrane is disposed between the anode chamber and the cathode chamber, a 3.5 N (N) aqueous sodium chloride solution is supplied to the anode chamber, and the cathode chamber is 10.8 N (N) aqueous sodium hydroxide solution is supplied, electrolysis is performed for 7 days under the conditions of an electrolysis temperature of 85 ° C. and a current density of 6 kA / m 2 . Here, the “ion cluster diameter of the layer B before electrolysis” means the ion cluster diameter of the layer B in the ion exchange membrane after the hydrolysis step in the production of an ion exchange membrane described later and before being used for electrolysis. I mean. “Ion cluster diameter of layer B after electrolysis” refers to the ion cluster diameter of layer B in the ion exchange membrane after electrolysis is performed under the above electrolysis condition (1). In this specification, [(ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis)] is simply “ratio of ion cluster diameter of layer B before and after electrolysis”. May be described.

電解前後の層Ｂのイオンクラスター径の比が、０．８３以上であると、電解中の電圧が高くなることを抑制し、電解性能の低下を抑制できる。この理由としては、以下に限定する趣旨ではないが、電解前の層Ｂのイオンクラスター径が大きくなり過ぎず、イオン交換膜の含水率増大による厚みの大幅な上昇を抑制できるからであると考えられる。電解前後の層Ｂのイオンクラスター径の比が、０．９５以下であると、電解中のイオン選択性が良好となる。この理由としては、以下に限定する趣旨ではないが、電解中の層Ｂのイオンクラスター径が最適な大きさに収縮するためであると考えられる。このような観点から、電解前後の層Ｂのイオンクラスター径の比は０．８３〜０．９５である。なお、電解前後の層Ｂのイオンクラスター径の比は、通電前の層Ｂのイオンクラスター径を大きくし、通電後の層Ｂのイオンクラスター径を小さくして、当該比を小さくする等の要領で、上記範囲に制御することができる。具体的には、例えば、後述する塩交換処理の処理温度を高くすることや、処理時間を長くすること等により、通電前の層Ｂのイオンクラスター径が大きくなる傾向にある。   When the ratio of the ion cluster diameters of the layer B before and after electrolysis is 0.83 or more, it is possible to suppress an increase in voltage during electrolysis and suppress degradation in electrolysis performance. The reason for this is not limited to the following, but is thought to be because the ion cluster diameter of the layer B before electrolysis does not become too large, and a significant increase in thickness due to an increase in the moisture content of the ion exchange membrane can be suppressed. It is done. When the ratio of the ion cluster diameters of the layer B before and after electrolysis is 0.95 or less, the ion selectivity during electrolysis is good. Although it is not the meaning limited to the following as this reason, it is thought that it is because the ion cluster diameter of the layer B in electrolysis shrink | contracts to the optimal magnitude | size. From such a viewpoint, the ratio of the ion cluster diameter of the layer B before and after electrolysis is 0.83 to 0.95. Note that the ratio of the ion cluster diameter of the layer B before and after electrolysis is such that the ion cluster diameter of the layer B before energization is increased, the ion cluster diameter of the layer B after energization is decreased, and the ratio is decreased. Thus, the above range can be controlled. Specifically, for example, the ion cluster diameter of the layer B before energization tends to be increased by increasing the treatment temperature of the salt exchange treatment described later, increasing the treatment time, or the like.

〔イオンクラスター径〕
電解前において、本実施形態のイオン交換膜における層Ａのイオンクラスター径は３．０〜４．５ｎｍであることが好ましく、３．２〜４．０ｎｍであることがより好ましく、３．４〜３．８ｎｍであることがさらに好ましい。電解前のイオン交換膜において、層Ｂのイオンクラスター径は２．５〜４．０ｎｍであることが好ましく、３．０〜３．８ｎｍであることがより好ましく、３．２〜３．６ｎｍであることがさらに好ましい。なお、層Ａが組成の異なる２層以上で構成される場合のイオンクラスター径は、それらの平均値とする。例えば、層Ａが層Ａ−１と層Ａ−２の２層からなる場合、層Ａ−１と層Ａ−２のイオンクラスター径のイオンクラスター径の平均値が３．０〜４．５ｎｍであることが好ましい。電解前のイオン交換膜中の層Ａ及び層Ｂのイオンクラスター径が上記範囲内にあると、イオン交換膜の電解性能及び強度がより向上する傾向にある。すなわち、上記の範囲の下限値よりもクラスター径が大きいと、強度がより向上する傾向にあり、上記の範囲の上限値よりもクラスター径が小さいと、電圧の上昇をより抑制できる傾向にある。なお、イオンクラスター径は、層Ａと層Ｂを剥離し、それぞれの層のみからなる単層膜に分離した後、得られた層Ａと層Ｂのフィルムを２５℃において水に含浸させた状態で、小角Ｘ線散乱（ＳＡＸＳ）により測定する。なお、イオン交換膜がコーティング層を有する場合、当該コーティング層をブラシで除去した後、それぞれの層のみからなる単層膜に分離することを除き、上記と同様にしてＳＡＸＳ測定に供することができる。詳細は、後述の実施例に記す。 [Ion cluster diameter]
Before electrolysis, the ion cluster diameter of the layer A in the ion exchange membrane of this embodiment is preferably 3.0 to 4.5 nm, more preferably 3.2 to 4.0 nm, and 3.4 to More preferably, it is 3.8 nm. In the ion exchange membrane before electrolysis, the ion cluster diameter of the layer B is preferably 2.5 to 4.0 nm, more preferably 3.0 to 3.8 nm, and 3.2 to 3.6 nm. More preferably it is. In addition, let the ion cluster diameter in case the layer A is comprised by two or more layers from which a composition differs be an average value thereof. For example, when layer A is composed of two layers, layer A-1 and layer A-2, the average value of the ion cluster diameters of the ion cluster diameters of layer A-1 and layer A-2 is 3.0 to 4.5 nm. Preferably there is. When the ion cluster diameters of the layer A and the layer B in the ion exchange membrane before electrolysis are within the above range, the electrolytic performance and strength of the ion exchange membrane tend to be further improved. That is, when the cluster diameter is larger than the lower limit value of the above range, the strength tends to be further improved, and when the cluster diameter is smaller than the upper limit value of the above range, an increase in voltage tends to be further suppressed. In addition, the ion cluster diameter is a state in which the layer A and the layer B are separated and separated into a single layer film composed only of each layer, and then the obtained film of the layer A and the layer B is impregnated with water at 25 ° C. And measured by small angle X-ray scattering (SAXS). In addition, when an ion exchange membrane has a coating layer, after removing the said coating layer with a brush, it isolate | separates into the single layer film which consists only of each layer, and can use for a SAXS measurement similarly to the above. . Details will be described in Examples described later.

本実施形態のイオン交換膜は、上記電解条件（１）での電解後、層Ｂのイオンクラスター径が２．０〜３．３ｎｍであることが好ましく、２．５〜３．２ｎｍであることがより好ましい。さらに、本実施形態のイオン交換膜は、電解性能と強度をより向上させる観点から、電解前の層Ｂのイオンクラスター径が２．５〜４．０ｎｍであり、かつ、電解後の層Ｂのイオンクラスター径が２．０〜３．３ｎｍであることがとりわけ好ましい。   In the ion exchange membrane of the present embodiment, after electrolysis under the above electrolysis condition (1), the ion cluster diameter of the layer B is preferably 2.0 to 3.3 nm, and preferably 2.5 to 3.2 nm. Is more preferable. Furthermore, in the ion exchange membrane of the present embodiment, from the viewpoint of further improving electrolysis performance and strength, the ion cluster diameter of the layer B before electrolysis is 2.5 to 4.0 nm, and the layer B after electrolysis It is particularly preferable that the ion cluster diameter is 2.0 to 3.3 nm.

〔イオン交換容量〕
本実施形態のイオン交換膜において、層Ａ及び層Ｂを構成する含フッ素重合体のイオン交換容量は、イオンクラスター径を制御する因子の一つである。含フッ素重合体のイオン交換容量とは、乾燥樹脂１ｇ当りの交換基の当量のことをいい、中和滴定によって測定することができる。層Ａを構成する含フッ素重合体Ａのイオン交換容量は、０．８〜１．２ミリ当量／ｇであることが好ましく、より好ましくは０．９〜１．１ミリ当量／ｇである。層Ｂを構成する含フッ素重合体Ｂのイオン交換容量は、０．７５ミリ当量／ｇ以上であることが好ましく、０．８１〜０．９８ミリ当量／ｇであることがより好ましい。含フッ素重合体のイオン交換容量が、上記範囲内であると、イオン交換膜の電解性能及び強度の低下がより効果的に抑制される傾向にある。また、層Ｂを構成する含フッ素重合体Ｂのイオン交換容量が０．８１以上であることにより、イオン交換膜中の含水率が高くなるので、電解した際にクラスター収縮が生じやすい。なお、各層のイオン交換容量が大きくなるほど、当該層のイオンクラスター径は大きくなり、イオン交換容量が小さくなるほどイオンクラスター径は小さくなる傾向にある。また、各層のイオン交換容量は、例えば、当該層に含まれる含フッ素重合体を構成する単量体の選択及び当該単量体の含有率により制御できる。具体的には、例えば、前述した一般式（１）〜（３）の仕込み比によって制御でき、より具体的には、イオン交換基を含む一般式（２），（３）で表される単量体の含有率が大きくなるほど、イオン交換容量は大きくなる傾向にある。 [Ion exchange capacity]
In the ion exchange membrane of the present embodiment, the ion exchange capacity of the fluoropolymer constituting the layer A and the layer B is one of the factors that control the ion cluster diameter. The ion exchange capacity of the fluoropolymer refers to the equivalent of exchange groups per gram of dry resin, and can be measured by neutralization titration. The ion exchange capacity of the fluoropolymer A constituting the layer A is preferably 0.8 to 1.2 meq / g, more preferably 0.9 to 1.1 meq / g. The ion exchange capacity of the fluoropolymer B constituting the layer B is preferably 0.75 meq / g or more, and more preferably 0.81 to 0.98 meq / g. When the ion exchange capacity of the fluoropolymer is in the above range, the electrolytic performance and strength of the ion exchange membrane tend to be more effectively suppressed. In addition, since the moisture content in the ion exchange membrane is high when the ion exchange capacity of the fluoropolymer B constituting the layer B is 0.81 or more, cluster shrinkage tends to occur during electrolysis. The larger the ion exchange capacity of each layer, the larger the ion cluster diameter of the layer, and the smaller the ion exchange capacity, the smaller the ion cluster diameter. In addition, the ion exchange capacity of each layer can be controlled by, for example, selection of a monomer constituting the fluoropolymer contained in the layer and the content of the monomer. Specifically, for example, it can be controlled by the above-mentioned preparation ratios of the general formulas (1) to (3), and more specifically, the simple formulas represented by the general formulas (2) and (3) containing ion exchange groups. The ion exchange capacity tends to increase as the content of the monomer increases.

〔強化芯材〕
本実施形態のイオン交換膜は、膜内に強化芯材３を含むことが好ましい。強化芯材は、イオン交換膜の強度及び寸法安定性を強化することができ、膜本体の内部に存在することが好ましい。強化芯材とは、強化糸を織った織布などであることが好ましい。強化芯材の材料は、長期にわたる耐熱性、耐薬品性が必要であることから、フッ素系重合体から成る繊維であることが好ましい。強化芯材の材料としては、特に限定されないが、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、トリフルオロクロルエチレン−エチレン共重合体及びフッ化ビニリデン重合体（ＰＶＤＦ）などが挙げられ、特にポリテトラフルオロエチレンから成る繊維を用いることが好ましい。 [Reinforced core material]
The ion exchange membrane of the present embodiment preferably includes the reinforcing core material 3 in the membrane. The reinforcing core material can enhance the strength and dimensional stability of the ion exchange membrane, and is preferably present inside the membrane body. The reinforcing core material is preferably a woven fabric woven with reinforcing yarn. The material of the reinforcing core material is preferably a fiber made of a fluorine-based polymer because long-term heat resistance and chemical resistance are required. The material of the reinforcing core material is not particularly limited. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), Examples thereof include tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF), and it is particularly preferable to use a fiber made of polytetrafluoroethylene.

強化芯材の糸径としては、好ましくは２０〜３００デニール、より好ましくは５０〜２５０デニール、織り密度（単位長さあたりの打ち込み本数）としては、好ましくは５〜５０本／インチである。強化芯材の形状としては、織布、不織布又は編布などが挙げられるが、織布の形態であることが好ましい。また、織布の厚みは、３０〜２５０μｍであることが好ましく、３０〜１５０μｍであることがより好ましい。   The yarn diameter of the reinforcing core is preferably 20 to 300 denier, more preferably 50 to 250 denier, and the weaving density (the number of driving per unit length) is preferably 5 to 50 / inch. Examples of the shape of the reinforcing core material include a woven fabric, a non-woven fabric, and a knitted fabric, but a woven fabric is preferable. Moreover, it is preferable that the thickness of a woven fabric is 30-250 micrometers, and it is more preferable that it is 30-150 micrometers.

織布または編布は、特に限定されないが、例えば、モノフィラメント、マルチフィラメントまたは、これらのヤーン、スリットヤーンなどが使用され、織り方は平織り、絡み織り、編織り、コード織り、シャーサッカなど種々の織り方が使用される。   The woven fabric or knitted fabric is not particularly limited. For example, monofilaments, multifilaments, yarns thereof, slit yarns, or the like are used. Is used.

また、強化芯材の開口率は、特に限定されないが、好ましくは３０％以上、より好ましくは５０％以上９０％以下である。開口率は、イオン交換膜としての電気化学的性質の観点から３０％以上、また、膜の機械的強度の観点から９０％以下が好ましい。開口率とは、イオン交換膜の表面積の合計（Ａ）に対するイオン交換膜においてイオン等の物質が通過できる面積の合計（Ｂ）の割合であり、（Ｂ）／（Ａ）で表される。（Ｂ）は、イオン交換膜において、イオンや電解液等が、イオン交換膜に含まれる強化芯材や強化糸等によって遮断されない領域の面積の合計である。開口率の測定方法は、下記のとおりである。イオン交換膜（コーティング等を塗る前の陽イオン交換膜）の表面画像を撮影し、強化芯材が存在しない部分の面積から、上記（Ｂ）が求められる。そして、イオン交換膜の表面画像の面積から上記（Ａ）を求め、上記（Ｂ）を上記（Ａ）で除することによって、開口率が求められる。   The opening ratio of the reinforcing core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of electrochemical properties as an ion exchange membrane, and 90% or less from the viewpoint of mechanical strength of the membrane. The aperture ratio is a ratio of the total area (B) through which substances such as ions can pass through the ion exchange membrane to the total surface area (A) of the ion exchange membrane, and is represented by (B) / (A). (B) is the total area of the regions in the ion exchange membrane where ions, electrolytes, etc. are not blocked by the reinforcing core material, reinforcing yarns, etc. contained in the ion exchange membrane. The method for measuring the aperture ratio is as follows. (B) is calculated | required from the area of the part in which the surface image of an ion exchange membrane (cation exchange membrane before applying a coating etc.) is not image | photographed and a reinforcement core material does not exist. And said (A) is calculated | required from the area of the surface image of an ion exchange membrane, and an aperture ratio is calculated | required by remove | dividing said (B) by said (A).

これら種々の強化芯材の中でも、特に好ましい形態としては、例えば、ＰＴＦＥから成る高強度多孔質シートをテープ状にスリットしたテープヤーン、又は、ＰＴＦＥから成る高度に配向したモノフィラメントの５０〜３００デニールを使用し、織り密度が１０〜５０本／インチの平織り構成からなり、更にその厚みは５０〜１００μｍの範囲でかつその開口率は６０％以上であることが好ましい。   Among these various reinforcing core materials, as a particularly preferable form, for example, a tape yarn obtained by slitting a high-strength porous sheet made of PTFE into a tape shape, or a highly oriented monofilament made of PTFE of 50 to 300 denier is used. It is preferably used and has a plain weave structure with a weave density of 10 to 50 pieces / inch, a thickness in the range of 50 to 100 μm, and an aperture ratio of 60% or more.

更に、織布には膜の製造工程において、強化芯材の目ズレを防止する目的で、通常犠牲芯材と呼ばれる補助繊維を含んでもよい。この犠牲芯材を含むことで、イオン交換膜内に連通孔２ａ，２ｂを形成することができる。   Furthermore, the woven fabric may contain auxiliary fibers, which are usually called sacrificial core materials, for the purpose of preventing misalignment of the reinforcing core materials in the membrane manufacturing process. By including this sacrificial core material, the communication holes 2a and 2b can be formed in the ion exchange membrane.

犠牲芯材は、膜の製造工程もしくは電解環境下において溶解性を有するものであり、特に限定されないが、レーヨン、ポリエチレンテレフタレート（ＰＥＴ）、セルロース及びポリアミドなどが用いられる。この場合の混織量は、好ましくは織布または編布全体の１０〜８０質量％、より好ましくは３０〜７０質量％である。   The sacrificial core material is soluble in the film production process or in an electrolytic environment, and is not particularly limited, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. The amount of the mixed woven fabric in this case is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the entire woven or knitted fabric.

〔連通孔〕
本実施形態のイオン交換膜は、膜内に連通孔２ａ，２ｂを有していてもよい。本実施形態において、連通孔とは、電解の際に発生する陽イオンや電解液の流路となり得る孔をいう。連通孔を形成することで、電解の際に発生するアルカリイオンや電解液の移動性がより向上する傾向にある。連通孔の形状は特に限定されないが、後述する製法によれば、連通孔の形成に用いられる犠牲芯材の形状とすることができる。 [Communication hole]
The ion exchange membrane of this embodiment may have communication holes 2a and 2b in the membrane. In the present embodiment, the communication hole refers to a hole that can serve as a flow path for cations generated during electrolysis or an electrolytic solution. By forming the communication hole, the mobility of alkali ions or electrolyte generated during electrolysis tends to be further improved. The shape of the communication hole is not particularly limited, but according to the manufacturing method described later, the shape of the sacrificial core material used for forming the communication hole can be obtained.

本実施形態において、連通孔は、強化芯材の陽極側（層Ａ側）と陰極側（層Ｂ側）を交互に通過するように形成されることが好ましい。このような構造とすることで、強化芯材の陰極側に連通孔が形成されている部分では、連通孔に満たされている電解液を通して輸送された陽イオン（例えば、ナトリウムイオン）が、強化芯材の陰極側にも流れることができる。その結果、陽イオンの流れが遮蔽されることがないため、イオン交換膜の電気抵抗を更に低減できる傾向にある。   In the present embodiment, the communication holes are preferably formed so as to alternately pass through the anode side (layer A side) and the cathode side (layer B side) of the reinforcing core material. By adopting such a structure, in the portion where the communication hole is formed on the cathode side of the reinforcing core material, the cation (for example, sodium ion) transported through the electrolyte filled in the communication hole is strengthened. It can also flow to the cathode side of the core material. As a result, since the cation flow is not shielded, the electric resistance of the ion exchange membrane tends to be further reduced.

〔コーティング〕
本実施形態のイオン交換膜は、必要に応じて陰極側及び陽極側にガス付着防止のためのコーティング層６，７を有していてもよい。コーティング層を構成する材料としては、特に限定されないが、ガス付着防止の観点から、無機物を含むことが好ましい。無機物としては、特に限定されないが、例えば、酸化ジルコニウム、酸化チタン等が挙げられる。コーティング層を形成する方法としては、特に限定されず、公知の方法を用いることができる。例えば、無機酸化物の微細粒子をバインダーポリマー溶液に分散した液を、スプレー等により塗布する方法が挙げられる。 〔coating〕
The ion exchange membrane of this embodiment may have coating layers 6 and 7 for preventing gas adhesion on the cathode side and the anode side as necessary. Although it does not specifically limit as a material which comprises a coating layer, It is preferable that an inorganic substance is included from a viewpoint of gas adhesion prevention. Although it does not specifically limit as an inorganic substance, For example, a zirconium oxide, a titanium oxide, etc. are mentioned. It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, a method in which a liquid in which fine particles of inorganic oxide are dispersed in a binder polymer solution is applied by spraying or the like can be used.

〔イオン交換膜の製造方法〕
本実施形態に係るイオン交換膜は、上記電解条件（１）での電解前後の、カルボン酸基を有する含フッ素重合体を含む層Ｂのイオンクラスター径の比を上記範囲内になるように制御して製造するため、含フッ素重合体Ａ及び含フッ素重合体Ｂのそれぞれのイオン交換容量、及び加水分解の条件等を調整する。以下、本実施形態のイオン交換膜の製造方法について詳細に説明する。 [Method for producing ion exchange membrane]
The ion exchange membrane according to this embodiment is controlled so that the ratio of the ion cluster diameter of the layer B containing the fluoropolymer having a carboxylic acid group before and after electrolysis under the electrolysis condition (1) is within the above range. Therefore, the ion exchange capacity and hydrolysis conditions of the fluoropolymer A and the fluoropolymer B are adjusted. Hereinafter, the manufacturing method of the ion exchange membrane of this embodiment is demonstrated in detail.

本実施形態のイオン交換膜の製造方法は、特に限定されないが、
１）イオン交換基、又は、加水分解によりイオン交換基となり得るイオン交換基前駆体を有する含フッ素重合体を製造する工程（重合体の製造工程）と、
２）犠牲糸を織り込んだ強化芯材を得る工程（強化芯材の製造工程）と、
３）イオン交換基、又は、加水分解によりイオン交換基となり得るイオン交換基前駆体を有する含フッ素重合体をフィルム化する工程（フィルム化工程）と、
４）前記強化芯材と、前記フィルムとを埋め込んで複合膜を形成する工程（埋め込み工程）と、
５）酸又はアルカリで、複合膜を加水分解する工程（加水分解工程）と、を含む製造方法が好ましい。
ここで、「イオン交換基」とは、スルホン酸基又はカルボン酸基のことをいう。 The method for producing the ion exchange membrane of the present embodiment is not particularly limited,
1) a step of producing a fluorine-containing polymer having an ion exchange group or an ion exchange group precursor that can be converted into an ion exchange group by hydrolysis (polymer production step);
2) A step of obtaining a reinforcing core material woven with sacrificial yarn (a manufacturing process of a reinforcing core material);
3) A step of forming a film of a fluoropolymer having an ion exchange group or an ion exchange group precursor that can be converted into an ion exchange group by hydrolysis (filming step);
4) A step of embedding the reinforcing core material and the film to form a composite film (embedding step);
5) A production method comprising hydrolyzing the composite membrane with an acid or an alkali (hydrolysis step) is preferable.
Here, the “ion exchange group” means a sulfonic acid group or a carboxylic acid group.

本実施形態のイオン交換膜は、上記の工程のうち、例えば、１）の重合体製造工程で含フッ素重合体のイオン交換容量を制御する、及び／又は、５）の加水分解工程で加水分解の条件を制御することにより、電解前後の層Ｂのイオンクラスター径の比を調整することができる。以下、各工程について説明する。   The ion exchange membrane of this embodiment controls the ion exchange capacity of the fluoropolymer in the polymer production process of 1) and / or hydrolysis in the hydrolysis process of 5) among the above processes, for example. By controlling the conditions, the ratio of the ion cluster diameters of the layer B before and after electrolysis can be adjusted. Hereinafter, each step will be described.

１）工程（重合体の製造工程）
層Ａを構成するスルホン酸基を有する含フッ素重合体Ａは、上記のとおり、例えば、第１群の単量体と第２群の単量体とを共重合する、又は第２群の単量体を単独重合することによって製造することができる。層Ｂを構成するカルボン酸基を有する含フッ素重合体Ｂは、例えば、上記のとおり、例えば、第１群の単量体と第３群の単量体とを共重合する、又は第３群の単量体を単独重合することによって製造することができる。重合方法は特に限定されないが、例えば、フッ化エチレン、特にテトラフルオロエチレンの重合に一般的用いられる重合方法を用いることができる。 1) Process (polymer production process)
As described above, the fluoropolymer A having a sulfonic acid group constituting the layer A is, for example, copolymerized with a first group of monomers and a second group of monomers, or with a second group of monomers. It can be produced by homopolymerizing the monomer. The fluorine-containing polymer B having a carboxylic acid group constituting the layer B is, for example, as described above, for example, copolymerizing a first group of monomers and a third group of monomers, or the third group. These monomers can be produced by homopolymerization. Although the polymerization method is not particularly limited, for example, a polymerization method generally used for polymerization of fluorinated ethylene, particularly tetrafluoroethylene can be used.

含フッ素重合体は、例えば、非水性法により得ることができる。非水性法においては、例えば、パーフルオロ炭化水素、クロロフルオロカーボン等の不活性溶媒を用い、パーフルオロカーボンパーオキサイドやアゾ化合物等のラジカル重合開始剤の存在下で、温度０〜２００℃、圧力０．１〜２０ＭＰａの条件下で、重合反応を行うことができる。   The fluoropolymer can be obtained, for example, by a non-aqueous method. In the non-aqueous method, for example, an inert solvent such as perfluorohydrocarbon or chlorofluorocarbon is used, and in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, the temperature is 0 to 200 ° C., the pressure is 0. The polymerization reaction can be performed under conditions of 1 to 20 MPa.

含フッ素重合体の製造において、上記単量体の組み合わせの種類及びその割合は、特に限定されず、得られる含フッ素系重合体に付与したい官能基の種類及び量等によって決定してよい。   In the production of the fluorinated polymer, the type of monomer combination and the ratio thereof are not particularly limited, and may be determined according to the type and amount of the functional group desired to be imparted to the resulting fluorinated polymer.

本実施形態において、含フッ素重合体のイオン交換容量を制御するために、各層を形成する含フッ素重合体の製造において、原料の単量体の混合比を調整してもよい。   In this embodiment, in order to control the ion exchange capacity of the fluoropolymer, the mixing ratio of the raw material monomers may be adjusted in the production of the fluoropolymer forming each layer.

層Ａを構成するスルホン酸基を有する含フッ素重合体Ａは、例えば、前記一般式（２）で表される単量体を重合して製造するか、又は、前記一般式（１）で表される単量体と、前記一般式（２）で表される単量体とを、以下のモル比で共重合して製造するのが好ましい。
前記一般式（１）で表される単量体：前記一般式（２）で表される単量体＝４：１〜７：１。 The fluoropolymer A having a sulfonic acid group constituting the layer A is produced, for example, by polymerizing the monomer represented by the general formula (2) or represented by the general formula (1). It is preferable that the monomer represented by the general formula (2) is copolymerized and produced at the following molar ratio.
Monomer represented by Formula (1): Monomer represented by Formula (2) = 4: 1 to 7: 1.

層Ｂを構成するカルボン酸基を有する含フッ素重合体Ｂは、例えば、前記一般式（３）で表される単量体を重合して製造するか、又は、前記一般式（１）で表される単量体と、前記一般式（３）で表される単量体とを、以下のモル比で共重合して製造されるのが好ましい。
前記一般式（１）で表される単量体：前記一般式（３）で表される単量体＝６：１〜９：１。 The fluoropolymer B having a carboxylic acid group constituting the layer B is produced, for example, by polymerizing the monomer represented by the general formula (3) or represented by the general formula (1). It is preferable that the monomer to be produced is copolymerized with the monomer represented by the general formula (3) at the following molar ratio.
Monomer represented by Formula (1): Monomer represented by Formula (3) = 6: 1 to 9: 1.

２）工程（強化芯材の製造工程）
本実施形態のイオン交換膜は、膜の強度をより向上させる観点から、強化芯材が膜内に埋め込まれていることが好ましい。連通孔を有するイオン交換膜とするときには、犠牲糸も一緒に強化芯材へ織り込む。この場合の犠牲糸の混織量は、好ましくは強化芯材全体の１０〜８０質量％、より好ましくは３０〜７０質量％である。犠牲糸としては、２０〜５０デニールの太さを有し、モノフィラメント又はマルチフィラメントからなるポリビニルアルコール等であることも好ましい。 2) Process (Manufacturing process of reinforced core material)
In the ion exchange membrane of the present embodiment, it is preferable that the reinforcing core material is embedded in the membrane from the viewpoint of further improving the strength of the membrane. When an ion exchange membrane having communication holes is used, the sacrificial yarn is also woven into the reinforcing core material. In this case, the blended amount of the sacrificial yarn is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the entire reinforcing core material. The sacrificial yarn is also preferably polyvinyl alcohol having a thickness of 20 to 50 denier and made of monofilament or multifilament.

３）工程（フィルム化工程）
前記１）工程で得られた含フッ素重合体を、フィルム化する方法は、特に限定されないが、押出し機を用いるのが好ましい。フィルム化する方法としては以下の方法が挙げられる。
層Ａと層Ｂがそれぞれ単層を構成する場合は、含フッ素重合体Ａ、含フッ素重合体Ｂをそれぞれ別々にフィルム化する方法が挙げられる。
層Ａが層Ａ−１と層Ａ−２からなる２層構造を有する場合は、含フッ素重合体Ａ−２と含フッ素重合体Ｂとを共押出しにより複合フィルムとし、別途、含フッ素重合体Ａ−１を単独でフィルム化する方法；又は含フッ素重合体Ａ−１と含フッ素重合体Ａ−２とを共押出しにより複合フィルムとし、別途、含フッ素重合体Ｂを単独でフィルム化する方法が挙げられる。これらのうち、含フッ素重合体Ａ−２と含フッ素重合体Ｂとを共押出しすると、界面の接着強度を高めることに寄与するため好ましい。 3) Process (filming process)
The method for forming the fluoropolymer obtained in the step 1) into a film is not particularly limited, but it is preferable to use an extruder. Examples of the method for forming a film include the following methods.
In the case where the layer A and the layer B each constitute a single layer, there can be mentioned a method in which the fluoropolymer A and the fluoropolymer B are formed into films separately.
When layer A has a two-layer structure consisting of layer A-1 and layer A-2, a fluoropolymer A-2 and a fluoropolymer B are co-extruded to form a composite film, and a separate fluoropolymer A method of forming A-1 alone; or a method of forming a composite film by coextrusion of fluoropolymer A-1 and fluoropolymer A-2, and separately forming fluoropolymer B alone. Is mentioned. Of these, co-extrusion of the fluoropolymer A-2 and the fluoropolymer B is preferable because it contributes to increasing the adhesive strength at the interface.

４）工程（埋め込み工程）
埋め込み工程においては、前記２）工程で得られた強化芯材、及び前記３）工程で得られたフィルムを、昇温したドラムの上で埋め込むのが好ましい。ドラム上では、透気性を有する耐熱性の離型紙を介して、各層を構成する含フッ素重合体が溶融する温度下で減圧により各層間の空気を除去しながら埋め込んで一体化することで、複合膜が得られる。ドラムとしては、特に限定されないが、例えば、加熱源及び真空源を有し、その表面に多数の細孔を有するものが挙げられる。 4) Process (embedding process)
In the embedding step, it is preferable to embed the reinforcing core material obtained in the step 2) and the film obtained in the step 3) on a heated drum. On the drum, through a heat-resistant release paper with air permeability, it is embedded and integrated while removing air between each layer by reducing the pressure at a temperature at which the fluoropolymer constituting each layer melts. A membrane is obtained. Although it does not specifically limit as a drum, For example, what has a heating source and a vacuum source and has many pores in the surface is mentioned.

強化芯材及びフィルムを積層する際の順番としては、前記３）工程に合わせて以下の方法が挙げられる。
層Ａと層Ｂがそれぞれ単層を構成する場合は、ドラムの上に、離型紙、層Ａのフィルム、強化芯材、層Ｂのフィルムの順に積層する方法が挙げられる。
層Ａが層Ａ−１と層Ａ−２からなる２層構造を有する場合は、ドラムの上に、離型紙、層Ａ−１のフィルム、強化芯材、層Ａ−２と層Ｂとの複合フィルムの順に積層する方法；又はドラムの上に、離型紙、層Ａ−１と層Ａ−２との複合フィルム、強化芯材、層Ｂの順に積層する方法が挙げられる。 Examples of the order of laminating the reinforcing core material and the film include the following methods in accordance with the step 3).
When each of the layers A and B constitutes a single layer, a method of laminating a release paper, a film of the layer A, a reinforcing core material, and a film of the layer B in this order on the drum can be mentioned.
When the layer A has a two-layer structure composed of the layer A-1 and the layer A-2, the release paper, the film of the layer A-1, the reinforcing core material, the layer A-2 and the layer B are formed on the drum. A method of laminating the composite film in this order; or a method of laminating the release paper, the composite film of the layer A-1 and the layer A-2, the reinforcing core material, and the layer B on the drum.

また、本実施形態のイオン交換膜の膜表面に凸部を設けるには、予めエンボス加工した離型紙を用いることによって、埋め込みの際に、溶融したポリマーからなる凸部を形成させることができる。   Moreover, in order to provide a convex part on the film | membrane surface of the ion exchange membrane of this embodiment, the convex part which consists of a molten polymer can be formed in the case of embedding by using the release paper embossed previously.

５）工程（加水分解工程）
前記４）工程で得られた複合膜を、酸又はアルカリによって加水分解を行う。この加水分解工程において、加水分解条件、例えば、溶液組成、加水分解温度、時間等を変えることによって、電解前後の層Ｂのイオンクラスター径の比を制御することができる。本実施形態に係るイオン交換膜の製造において、加水分解は、例えば、２．５〜４．０規定（Ｎ）の水酸化カリウム（ＫＯＨ）と２０〜４０質量％のＤＭＳＯ（Ｄｉｍｅｔｈｙｌ ｓｕｌｆｏｘｉｄｅ）の水溶液中、４０〜９０℃で、１０分〜２４時間行うことが好ましい。その後、５０〜９５℃の条件下、０．５〜０．７規定（Ｎ）苛性ソーダ（ＮａＯＨ）溶液を用いて塩交換処理を行うことが好ましい。なお、層厚の過度な増大に起因する電圧上昇をより効果的に防止する観点から、上記塩交換処理における処理温度を７０℃以上とする場合は、処理時間を２時間未満とすることが好ましい。 5) Process (hydrolysis process)
The composite membrane obtained in the step 4) is hydrolyzed with acid or alkali. In this hydrolysis step, the ratio of the ion cluster diameters of the layer B before and after electrolysis can be controlled by changing the hydrolysis conditions such as the solution composition, hydrolysis temperature, time and the like. In the production of the ion exchange membrane according to the present embodiment, the hydrolysis is performed, for example, with an aqueous solution of 2.5 to 4.0 N (N) potassium hydroxide (KOH) and 20 to 40% by mass of DMSO (dimethylsulfoxide). It is preferable to carry out at 40-90 degreeC for 10 minutes-24 hours. Thereafter, it is preferable to carry out a salt exchange treatment using a 0.5 to 0.7 N (N) sodium hydroxide (NaOH) solution under the condition of 50 to 95 ° C. In addition, from the viewpoint of more effectively preventing a voltage increase due to an excessive increase in the layer thickness, when the treatment temperature in the salt exchange treatment is 70 ° C. or higher, the treatment time is preferably less than 2 hours. .

なお、イオンクラスター径は、加水分解工程を行う液の組成、温度、時間等を変えることにより制御できる。例えば、イオンクラスター径を大きくさせる場合、ＫＯＨ濃度を低下させる、ＤＭＳＯ濃度を上昇させる、加水分解温度を上昇させる、又は加水分解時間を長くすることにより達成できる。各層のイオンクラスター径を制御することにより、電解前後の層Ｂのイオンクラスター径の比も制御することができ、電解後の層Ｂのクラスター径を電解前に比べて大幅に小さくすることもできる。具体的には、例えば、電解前の層Ｂのイオンクラスター径が大きくなるように制御すると、電解前後の層Ｂのイオンクラスター径の比が小さくなる。また、加水分解した膜の表面にコーティング層を設けてもよい。   The ion cluster diameter can be controlled by changing the composition, temperature, time, etc. of the liquid used in the hydrolysis step. For example, when increasing the ion cluster diameter, it can be achieved by decreasing the KOH concentration, increasing the DMSO concentration, increasing the hydrolysis temperature, or lengthening the hydrolysis time. By controlling the ion cluster diameter of each layer, the ratio of the ion cluster diameter of the layer B before and after electrolysis can also be controlled, and the cluster diameter of the layer B after electrolysis can be made much smaller than before electrolysis. . Specifically, for example, when the ion cluster diameter of the layer B before electrolysis is controlled to be large, the ratio of the ion cluster diameter of the layer B before and after electrolysis becomes small. A coating layer may be provided on the surface of the hydrolyzed membrane.

〔電解槽〕
本実施形態の電解槽は、本実施形態のイオン交換膜を備える。図２に本実施形態の電解槽の一例の模式図を示す。電解槽１３は、陽極１１と、陰極１２と、陽極と陰極との間に配置された、本実施形態のイオン交換膜１と、を少なくとも備える。電解槽は、種々の電解に使用できるが、以下、代表例として、塩化アルカリ水溶液の電解に使用する場合について説明する。 [Electrolysis tank]
The electrolytic cell of this embodiment includes the ion exchange membrane of this embodiment. FIG. 2 shows a schematic diagram of an example of the electrolytic cell of the present embodiment. The electrolytic cell 13 includes at least the anode 11, the cathode 12, and the ion exchange membrane 1 of this embodiment disposed between the anode and the cathode. Although an electrolytic cell can be used for various electrolysis, the case where it is used for electrolysis of aqueous alkali chloride solution is demonstrated as a typical example below.

電解条件は、特に限定されず、公知の条件で行うことができる。例えば、陽極室に２．５〜５．５規定（Ｎ）の塩化アルカリ水溶液を供給し、陰極室は水又は希釈した水酸化アルカリ水溶液を供給し、電解温度が５０〜１２０℃、電流密度が０．５〜１０ｋＡ／ｍ2の条件で電解することができる。 Electrolysis conditions are not particularly limited, and can be performed under known conditions. For example, 2.5 to 5.5 normal (N) alkali chloride aqueous solution is supplied to the anode chamber, water or diluted alkali hydroxide aqueous solution is supplied to the cathode chamber, the electrolysis temperature is 50 to 120 ° C., and the current density is Electrolysis can be performed under conditions of 0.5 to 10 kA / m 2 .

本実施形態の電解槽の構成は、特に限定されず、例えば、単極式でも複極式でもよい。電解槽を構成する材料としては、特に限定されないが、例えば、陽極室の材料としては、塩化アルカリ及び塩素に耐性があるチタン等が好ましく、陰極室の材料としては、水酸化アルカリ及び水素に耐性があるニッケル等が好ましい。電極の配置は、イオン交換膜と陽極との間に適当な間隔を設けて配置してもよいが、陽極とイオン交換膜が接触して配置されていてもよい。また、陰極は一般的にはイオン交換膜と適当な間隔を設けて配置されているが、この間隔がない接触型の電解槽（ゼロギャップ式電解槽）であってもよい。   The structure of the electrolytic cell of this embodiment is not specifically limited, For example, a monopolar type or a bipolar type may be sufficient. The material constituting the electrolytic cell is not particularly limited. For example, the material for the anode chamber is preferably titanium or the like resistant to alkali chloride and chlorine, and the material for the cathode chamber is resistant to alkali hydroxide and hydrogen. Nickel or the like is preferred. The electrode may be arranged with an appropriate interval between the ion exchange membrane and the anode, but the anode and the ion exchange membrane may be arranged in contact with each other. Further, the cathode is generally arranged with an appropriate interval from the ion exchange membrane, but a contact type electrolytic cell (zero gap electrolytic cell) without this interval may be used.

以下、実施例により本実施形態を詳細に説明する。なお、本実施形態は以下の実施例に限定されるものではない。   Hereinafter, the present embodiment will be described in detail by way of examples. Note that the present embodiment is not limited to the following examples.

実施例及び比較例における各測定方法は以下のとおりである。
［イオンクラスター径の測定方法］
イオンクラスター径は小角Ｘ線散乱（ＳＡＸＳ）により測定した。ＳＡＸＳ測定はイオン交換膜がコーティング層を有する場合はコーティング層をブラシで除去した後、層Ａと層Ｂを剥離し、それぞれの層のみからなる単層膜について、２５℃において水に含浸させた状態で測定を行った。ＳＡＸＳ測定は、リガク製ＳＡＸＳ装置ＮａｎｏＶｉｅｗｅｒを用いた。小角領域は試料―検出器間距離８４１ｍｍで検出器としてＰＩＬＡＴＵＳ１００Ｋを用い、広角領域は試料―検出器間距離７５ｍｍ、検出器にイメージングプレートを用いて測定を行い、両プロフィールを合体させることにより０．１°＜散乱角（２θ）＜３０°の範囲の散乱角における散乱データを得た。試料は７枚重ねた状態で測定を行い、露光時間は小角領域、広角領域測定とも１５分とした。二次元検出器によりデータを取得した場合には円環平均等合理的な手法によりデータを一次元化した。得られたＳＡＸＳプロフィールに対しては、検出器の暗電流補正等、検出器に由来する補正、試料以外の物質による散乱に対する補正（空セル散乱補正）を実施した。ＳＡＸＳプロフィールに対するＸ線ビーム形状の影響（スメアの影響）が大きい場合はＸ線ビーム形状に対する補正（デスメア）も行った。こうして得られた一次元ＳＡＸＳプロフィールに対し、橋本康博、坂本直紀、飯嶋秀樹 高分子論文集 ｖｏｌ．６３ Ｎｏ．３ ｐｐ．１６６ ２００６に記載された手法に準じてイオンクラスター径を求めた。すなわち、イオンクラスター構造が粒径分布を持つコアーシェル型の剛体球で表されると仮定し、このモデルに基づく理論散乱式を用いて実測のＳＡＸＳプロフィールのイオンクラスター由来の散乱が支配的な散乱角領域のＳＡＸＳプロフィールをフィッティングすることで平均クラスター直径（イオンクラスター径）、イオンクラスター個数密度を求めた。このモデルにおいて、コアの部分がイオンクラスターに相当し、コアの直径がイオンクラスター径となるものとした。なお、シェル層は仮想的なものでシェル層の電子密度はマトリックス部分と同じとした。またここではシェル層厚みは０．２５ｎｍとした。フィッティングに用いるモデルの理論散乱式を次の式（Ａ）に示す。また、フィッティング範囲は１．４＜２θ＜６．７°とした。 Each measuring method in an Example and a comparative example is as follows.
[Measurement method of ion cluster diameter]
The ion cluster diameter was measured by small angle X-ray scattering (SAXS). In the SAXS measurement, when the ion exchange membrane has a coating layer, the coating layer was removed with a brush, and then the layer A and the layer B were peeled off, and a single-layer membrane composed only of each layer was impregnated with water at 25 ° C. Measurements were made in the state. The SAXS measurement was performed using a Rigaku SAXS device NanoViewer. The small-angle region was measured using a sample-detector distance of 841 mm and PILATUS100K as the detector, and the wide-angle region was measured using a sample-detector distance of 75 mm using an imaging plate as the detector. Scattering data was obtained at scattering angles in the range of 1 ° <scattering angle (2θ) <30 °. Measurement was performed with seven samples stacked, and the exposure time was 15 minutes for both the small-angle and wide-angle measurement. When data was acquired by a two-dimensional detector, the data was made one-dimensional by a rational method such as an annular average. The obtained SAXS profile was subjected to correction derived from the detector, such as correction of the dark current of the detector, and correction for scattering by substances other than the sample (empty cell scattering correction). When the influence of the X-ray beam shape (the effect of smear) on the SAXS profile was large, correction (desmear) for the X-ray beam shape was also performed. For the one-dimensional SAXS profile obtained in this way, Yasuhiro Hashimoto, Naoki Sakamoto, Hideki Iijima Polymer Papers vol. 63 No. 3 pp. 166 The ion cluster diameter was determined according to the method described in 2006. That is, assuming that the ion cluster structure is represented by a core-shell type hard sphere having a particle size distribution, the scattering angle from which scattering from the ion cluster of the measured SAXS profile is dominant using the theoretical scattering formula based on this model. The average cluster diameter (ion cluster diameter) and ion cluster number density were determined by fitting the SAXS profile of the region. In this model, the core portion corresponds to the ion cluster, and the core diameter is the ion cluster diameter. The shell layer is virtual and the electron density of the shell layer is the same as that of the matrix portion. Here, the thickness of the shell layer was 0.25 nm. The following formula (A) shows the theoretical scattering formula of the model used for fitting. The fitting range was 1.4 <2θ <6.7 °.

上記において、Ｃは定数、Ｎはクラスター個数密度、ηはコア、つまりイオンクラスター部分とその周りの仮想的なシェルを剛体球と仮定した場合のその体積分率、θはブッラグ角、λは用いるＸ線波長、ｔはシェル層厚み、ａ0は平均イオンクラスター半径、Γ（ｘ）はガンマ関数、σはイオンクラスター半径（コア半径）の標準偏差を示す。Ｐ（ａ）はコア半径ａの分布関数を表し、ここではａの体積分布がＳｃｈｕｌｔｚ−Ｚｉｍｍ分布ｐ（ａ）に従うとする。Ｍは分布を表すパラメータである。Ｉｂ（ｑ）は測定時の過剰な水由来の散乱、熱散漫散乱を含むバックグラウンド散乱を表しており，ここでは定数と仮定する。フィッティングの際には上記パラメータのうち、Ｎ、η、ａ0、σ、Ｉｂ（ｑ）を可変パラメータとする。なお、本明細書において、イオンクラスター径とは、イオンクラスターの平均直径（２ａ0）を意味する。 In the above, C is a constant, N is the cluster number density, η is the volume fraction when assuming the core, that is, the ionic cluster portion and the surrounding virtual shell as a hard sphere, θ is the Bragg angle, and λ is used. X-ray wavelength, t is shell layer thickness, a 0 is an average ion cluster radius, Γ (x) is a gamma function, and σ is a standard deviation of the ion cluster radius (core radius). P (a) represents a distribution function of the core radius a. Here, it is assumed that the volume distribution of a follows the Schultz-Zimm distribution p (a). M is a parameter representing the distribution. Ib (q) represents background scattering including scattering from excess water and thermal diffuse scattering at the time of measurement, and is assumed to be a constant here. At the time of fitting, among the above parameters, N, η, a 0 , σ, and Ib (q) are set as variable parameters. In the present specification, the ion cluster diameter means an average diameter (2a 0 ) of the ion cluster.

［加水分解工程後の各層の厚みの測定方法］
加水分解工程後であって、電解前のイオン交換膜の、層Ａ−１側、又は層Ｂ側から断面方向へ幅約１００μｍで切り落とし、含水した状態で断面を上部に向けて光学顕微鏡を用いて厚みを実測した。その際、切り落とす部分は隣り合う強化芯材の中間部分（谷部）であり、得られた断面図において測定する箇所は、図１で示すと、隣り合う強化芯材３の中間部分であり、（α）から（β）へ向かう方向を厚み方向として層Ａと層Ｂの厚みを測定した。 [Method for measuring thickness of each layer after hydrolysis step]
After the hydrolysis step, the ion exchange membrane before electrolysis is cut off from the layer A-1 side or the layer B side in a cross-sectional direction with a width of about 100 μm, and in a water-containing state, the cross-section is directed to the top, and an optical microscope is used. The thickness was measured. At that time, the part to be cut off is an intermediate part (valley part) of the adjacent reinforcing core material, and the location to be measured in the obtained cross-sectional view is an intermediate part of the adjacent reinforcing core material 3 as shown in FIG. The thicknesses of layer A and layer B were measured with the direction from (α) to (β) as the thickness direction.

［電解性能評価］
電解槽として、図２に示す電解槽１３の構成を次のように変更したゼロギャップ電解槽を用いた。すなわち、電解槽１３におけるイオン交換膜１と陽極１１及び陰極１２との位置関係を、イオン交換膜１と陽極１１とが接した状態及びイオン交換膜１と陰極１２とが接した状態（いわゆる「ゼロギャップ」の状態）となるように変更した電解槽を用意した。このゼロギャップ電解槽を用いて、下記の条件で電解を行い、電解電圧、電流効率、生成する苛性ソーダ中の塩化ナトリウム量に基づいて電解性能を評価した。なお、イオン交換膜が陰極及び陽極の電極表面全体で接する場合も、電極表面のある点で接する場合も、ゼロギャップの状態であるものとした。
陽極側に塩化ナトリウムの濃度が３．５規定（Ｎ）の濃度となるように調整しつつ食塩水を供給し、陰極側の苛性ソーダ濃度を１０．８規定（Ｎ）に保ちつつ水を供給した。食塩水の温度を８５℃に設定して、６ｋＡ／ｍ2の電流密度で、電解槽の陰極側の液圧が陽極側の液圧よりも５．３ｋＰａ高い条件で電解を行った。
電解７日間の苛性ソーダに含まれる塩化ナトリウムの濃度をＪＩＳ規格Ｋ１２００−３−１の方法で測定した。電解生成した苛性ソーダに硝酸を加えて中和し、硫酸鉄（ＩＩＩ）アンモニウム溶液、チオシアン酸水銀（ＩＩ）を加え、溶液を呈色させた。その溶液をＵＶ計により吸光光度分析することによって苛性ソーダ中の塩化ナトリウム濃度を測定し、７日目の測定値を苛性ソーダ中の塩化ナトリウム濃度として求めた。ＵＶ計には、ＪＡＳＣＯ製Ｖ−６３０ｓｐｅｔｒｏｐｈｏｔｏｍｅｔｅｒを用いた。
また、電流効率は、生成された苛性ソーダの質量、濃度を測定し、一定時間に生成された苛性ソーダのモル数を、その間に流れた電流の電子のモル数で除することで求めた。 [Electrolytic performance evaluation]
As the electrolytic cell, a zero gap electrolytic cell in which the configuration of the electrolytic cell 13 shown in FIG. 2 was changed as follows was used. That is, the positional relationship between the ion exchange membrane 1 and the anode 11 and the cathode 12 in the electrolytic cell 13 is such that the ion exchange membrane 1 and the anode 11 are in contact with each other and the ion exchange membrane 1 and the cathode 12 are in contact with each other (so-called “ An electrolytic cell was prepared so as to be in a “zero gap” state). Using this zero gap electrolytic cell, electrolysis was performed under the following conditions, and the electrolysis performance was evaluated based on the electrolysis voltage, current efficiency, and the amount of sodium chloride in the sodium hydroxide produced. In addition, the case where the ion exchange membrane is in contact with the entire electrode surface of the cathode and the anode or in contact with a certain point on the electrode surface is in a zero gap state.
Salt water was supplied to the anode side while adjusting the sodium chloride concentration to be 3.5 N (N), and water was supplied while maintaining the sodium hydroxide concentration at 10.8 N (N). . The temperature of the saline solution was set to 85 ° C., and electrolysis was performed at a current density of 6 kA / m 2 and a condition that the liquid pressure on the cathode side of the electrolytic cell was 5.3 kPa higher than the liquid pressure on the anode side.
The concentration of sodium chloride contained in caustic soda for 7 days of electrolysis was measured by the method of JIS standard K1200-3-1. The electrolytically generated caustic soda was neutralized by adding nitric acid, and an iron (III) sulfate ammonium solution and mercury (II) thiocyanate were added to color the solution. The solution was subjected to spectrophotometric analysis with a UV meter to measure the sodium chloride concentration in caustic soda, and the measurement value on day 7 was determined as the sodium chloride concentration in caustic soda. A JASCO V-630 spectrophotometer was used as the UV meter.
The current efficiency was determined by measuring the mass and concentration of the produced caustic soda and dividing the number of moles of caustic soda produced in a certain period of time by the number of moles of electrons flowing during that time.

［強度試験］
強度試験としては、加水分解後（電解前）のイオン交換膜を用い、ＪＩＳＫ６７３２に準じて引張強度及び引張伸度の測定を行った。 [Strength test]
As a strength test, tensile strength and tensile elongation were measured according to JISK6732, using an ion exchange membrane after hydrolysis (before electrolysis).

［実施例１］
含フッ素重合体Ａ−１として、下記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と下記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。なお、イオン交換容量は中和滴定で確認した。以下の実施例及び比較例でも同様にイオン交換容量を確認した。
ＣＦ2＝ＣＸ1Ｘ2 （１）
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）a−Ｏ−（ＣＦ2）b−ＳＯ2Ｆ （２） [Example 1]
As the fluoropolymer A-1, monomers represented by the following general formula (1) (X 1 = F, X 2 = F) and monomers represented by the following general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g. The ion exchange capacity was confirmed by neutralization titration. The ion exchange capacity was similarly confirmed in the following examples and comparative examples.
CF 2 = CX 1 X 2 (1)
CF 2 = CF- (OCF 2 CYF ) a -O- (CF 2) b -SO 2 F (2)

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と下記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．５：１で共重合し、イオン交換容量が０．８９ｍ当量／ｇのポリマーを得た。
ＣＦ2＝ＣＦ−（ＯＣＦ2ＣＹＦ）c−Ｏ−（ＣＦ2）d−ＣＯＯＲ （３） As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the following general formula (3) (c) = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 7.5: 1, a polymer having an ion exchange capacity of 0.89 meq / g was obtained.
CF 2 = CF- (OCF 2 CYF ) c -O- (CF 2) d -COOR (3)

なお、含フッ素重合体Ａ（Ａ−１、Ａ−２）は、より詳細には、以下に示す溶液重合により作製した。
まず、ステンレス製２０ＬオートクレーブにＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）2ＣＯＯＣＨ3とＨＦＣ−４３−１０ｍｅｅ溶液を仕込み、容器内を充分に窒素置換した後、さらにＣＦ2＝ＣＦ2（ＴＦＥ）で置換し、容器内の温度が３５℃で安定になるまで加温してＴＦＥで加圧した。
次いで、重合開始剤として（ＣＦ3ＣＦ2ＣＦ2ＣＯＯ）2の５％ＨＦＣ４３−１０ｍｅｅ溶液を入れて、反応を開始した。この際、連鎖移動剤としてメタノールを加えた。３５℃で攪拌しながらＴＦＥを断続的にフィードしつつ、途中でメタノールを入れ、ＴＦＥ圧力を降下させて、ＴＦＥを所定量供給したところで重合を停止した。未反応ＴＦＥを系外に放出した後、得られた重合液にメタノールを加えて含フッ素系重合体を凝集、分離した。さらに、乾燥した後、重合体Ａを得た。得られた含フッ素系重合体は２軸押出し機にてペレット化した。
また、含フッ素重合体Ｂは、ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）2ＣＯＯＣＨ3の代わりにＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）2ＳＯ2Ｆを仕込み、連鎖移動剤を使用せず、途中でメタノールの代わりに（ＣＦ3ＣＦ2ＣＦ2ＣＯＯ）2の５％ＨＦＣ４３−１０ｍｅｅ溶液を加える以外は重合体Ａと同様の方法で得た。以下の実施例及び比較例でも同様に含フッ素重合体Ａ及びＢのペレットを得た。 In more detail, the fluorinated polymer A (A-1, A-2) was produced by the solution polymerization shown below.
First, CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 COOCH 3 and HFC-43-10mee solution are charged into a stainless steel 20 L autoclave, and the inside of the container is sufficiently purged with nitrogen, and then CF 2 = CF 2 (TFE) was substituted, and the container was heated until the temperature in the container became stable at 35 ° C. and pressurized with TFE.
Then placed as a polymerization initiator (CF 3 CF 2 CF 2 COO ) 2 in 5% HFC43-10mee solution to start the reaction. At this time, methanol was added as a chain transfer agent. While TFE was intermittently fed while stirring at 35 ° C., methanol was added on the way, the TFE pressure was lowered, and the polymerization was stopped when a predetermined amount of TFE was supplied. After releasing unreacted TFE out of the system, methanol was added to the resulting polymerization solution to aggregate and separate the fluorinated polymer. Further, after drying, a polymer A was obtained. The obtained fluorine-containing polymer was pelletized with a twin screw extruder.
In addition, the fluoropolymer B contains CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 COOCH 3 instead of CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 2 F. It was obtained in the same manner as the polymer A, except that a 5% HFC43-10mee solution of (CF 3 CF 2 CF 2 COO) 2 was added in the middle of the process without using a charge and a chain transfer agent. In the following examples and comparative examples, pellets of fluoropolymers A and B were obtained in the same manner.

得られたフッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ１）を得た。該フィルム（ａ１）の断面を光学顕微鏡で観察した結果、層Ａ−２の厚みが８０μｍ、層Ｂの厚みが１３μｍであった。なお、層Ａ−２と層Ｂとは偏光をかけることによって区別した。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ１）を得た。   The obtained fluoropolymer A-2 and fluoropolymer B were co-extruded by means of an apparatus equipped with two extruders, a two-layer co-extrusion T-die, and a take-out machine. A layer film (a1) was obtained. As a result of observing the cross section of the film (a1) with an optical microscope, the thickness of the layer A-2 was 80 μm, and the thickness of the layer B was 13 μm. Layer A-2 and layer B were distinguished by applying polarized light. Moreover, the single layer film (b1) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ１）、強化芯材、２層フィルム（ａ１）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。   On the drum that has a heating source and a vacuum source inside, and has a large number of fine holes on the surface, air-permeable heat-resistant release paper, single-layer film (b1), reinforced core material, two-layer film (a1) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane.

強化芯材として、ポリテトラフルオロエチレン（ＰＴＦＥ）製１００デニールのテープヤーンに９００回／ｍの撚りをかけ糸状としたものと、補助繊維（犠牲糸）の経糸として３０デニール、６フィラメントのポリエチレンテレフタレート（ＰＥＴ）を２００回／ｍの撚りをかけたもの、緯糸として３５デニール、８フィラメントのＰＥＴ製の糸に１０回／ｍの撚りをかけたものを準備し、これらの糸をＰＴＦＥ糸が２４本／インチ、犠牲糸がＰＴＦＥに対して４倍の６４本／インチとなるよう交互配列で平織りして厚み１００μｍの織布を得た。得られた織布を加熱された金属ロールで圧着し織布の厚みを７０μｍに調製した。このとき、ＰＴＦＥ糸のみの開口率は７５％であった。   As a reinforcing core material, a polytetrafluoroethylene (PTFE) 100-denier tape yarn twisted 900 times / m to form a yarn, and a 30-denier, 6-filament polyethylene terephthalate as an auxiliary fiber (sacrificial yarn) warp (PET) with a twist of 200 times / m, 35 denier as a weft, 8 filaments of PET made with a twist of 10 times / m were prepared, and these yarns were 24 PTFE yarns. Plain weave was used in an alternating arrangement so that the number of sacrificial yarns was 64 / inch, which is 4 times that of PTFE, and a woven fabric having a thickness of 100 μm was obtained. The obtained woven fabric was pressure-bonded with a heated metal roll to adjust the thickness of the woven fabric to 70 μm. At this time, the opening ratio of only the PTFE yarn was 75%.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で８０℃の温度で０．５時間加水分解し、その後、５０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて１時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 80 ° C. for 0.5 hour, and then 0.6 N (N) under the condition of 50 ° C. Salt exchange treatment was performed using NaOH solution for 1 hour.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９１であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.91. The measurement results are shown in Table 1.

［実施例２］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Example 2]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体と前記一般式（２）（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）で表わされる単量体とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, a monomer represented by the general formula (1) and a monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) Copolymerization was performed at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．５：１で共重合し、イオン交換容量が０．８９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (3) (c = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 7.5: 1, a polymer having an ion exchange capacity of 0.89 meq / g was obtained.

得られたフッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ２）を得た。該フィルムの断面を光学顕微鏡で観察した結果、層Ａ−２の厚みが８０μｍ、層Ｂの厚みが１３μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ２）を得た。   The obtained fluoropolymer A-2 and fluoropolymer B were co-extruded by means of an apparatus equipped with two extruders, a two-layer co-extrusion T-die, and a take-out machine. A layer film (a2) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of layer A-2 was 80 μm, and the thickness of layer B was 13 μm. Moreover, the single layer film (b2) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ２）、強化芯材、２層フィルム（ａ２）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材としては、実施例１と同様のものを用いた。   On the drum with a heating source and a vacuum source inside, and a large number of fine holes on the surface, air-permeable heat-resistant release paper, single layer film (b2), reinforced core material, two-layer film (a2) And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. As the reinforcing core material, the same material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で５０℃の温度で２４時間加水分解し、その後、９０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて０．５時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) KOH at a temperature of 50 ° C. for 24 hours, and then a 0.6 N (N) NaOH solution under the condition of 90 ° C. A salt exchange treatment was performed for 0.5 hour.

水とエタノールの５０／５０質量部の混合溶液にイオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 = CF 2 and CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluoropolymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９３であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.93. The measurement results are shown in Table 1.

［実施例３］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Example 3]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

含フッ素重合体層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．３：１で共重合し、イオン交換容量が０．９１ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the fluoropolymer layer B, the monomer (X 1 = F, X 2 = F) represented by the general formula (1) and the single unit represented by the general formula (3) are used. The polymer (c = 1, d = 2, Y = CF 3 , R = CH 3 ) was copolymerized at a molar ratio of 7.3: 1 to obtain a polymer having an ion exchange capacity of 0.91 meq / g. .

フッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ３）を得た。該フィルムの断面を光学顕微鏡で観察した結果、含フッ素重合体層Ａ−２の厚みが８０μｍ、含フッ素重合体層Ｂの厚みが１３μｍであった。また、単層Ｔダイにて厚み２０μｍの含フッ素重合体層Ａ−１の単層フィルム（ｂ３）を得た。   Fluoropolymer A-2 and fluoropolymer B were co-extruded with an apparatus equipped with two extruders, two-layer co-extrusion T-die, and a take-out machine, and a two-layer film having a thickness of 93 μm ( a3) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of the fluoropolymer layer A-2 was 80 μm, and the thickness of the fluoropolymer layer B was 13 μm. Moreover, the single layer film (b3) of the fluoropolymer layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ３）、強化芯材、２層フィルム（ａ３）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材としては、実施例１と同様のものを用いた。   On the drum that has a heating source and a vacuum source inside, and has a large number of fine holes on the surface, air-permeable heat-resistant release paper, single-layer film (b3), reinforced core material, two-layer film (a3) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. As the reinforcing core material, the same material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で５０℃の温度で２４時間加水分解し、その後、９５℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて１時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) KOH at a temperature of 50 ° C. for 24 hours, and then a 0.6 N (N) NaOH solution under the condition of 95 ° C. The salt exchange treatment was performed for 1 hour.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加えボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．８６であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.86. The measurement results are shown in Table 1.

［実施例４］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Example 4]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比６：１で共重合し、イオン交換容量が０．９５ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 6: 1 to obtain a polymer having an ion exchange capacity of 0.95 meq / g.

含フッ素重合体層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比８：１で共重合し、イオン交換容量が０．８５ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the fluoropolymer layer B, the monomer (X 1 = F, X 2 = F) represented by the general formula (1) and the single unit represented by the general formula (3) are used. The polymer (c = 1, d = 2, Y = CF 3 , R = CH 3 ) was copolymerized at a molar ratio of 8: 1 to obtain a polymer having an ion exchange capacity of 0.85 meq / g.

フッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み１００μｍの２層フィルム（ａ４）を得た。該フィルムの断面を光学顕微鏡で観察した結果、含フッ素重合体層Ａ−２の厚みが８５μｍ、含フッ素重合体層Ｂの厚みが１５μｍであった。また、単層Ｔダイにて厚み２５μｍの含フッ素重合体層Ａ−１の単層フィルム（ｂ４）を得た。   Fluoropolymer A-2 and fluoropolymer B were co-extruded with two extruders, a two-layer co-extrusion T-die, and an apparatus equipped with a take-out machine to form a two-layer film (100 μm thick) a4) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of the fluoropolymer layer A-2 was 85 μm, and the thickness of the fluoropolymer layer B was 15 μm. Moreover, the single layer film (b4) of the fluoropolymer layer A-1 with a thickness of 25 micrometers was obtained with the single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ４）、強化芯材、２層フィルム（ａ４）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材としては、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and having a large number of fine holes on the surface, air-permeable heat-resistant release paper, single-layer film (b4), reinforced core material, two-layer film (a4) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. As the reinforcing core material, the same material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で８０℃の温度で０．５時間加水分解し、その後、５０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて１時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 80 ° C. for 0.5 hour, and then 0.6 N (N) under the condition of 50 ° C. Salt exchange treatment was performed using NaOH solution for 1 hour.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加えボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９３であった。測定結果を表１に示す。
［実施例５］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.93. The measurement results are shown in Table 1.
[Example 5]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．５：１で共重合し、イオン交換容量が０．８９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (3) (c = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 7.5: 1, a polymer having an ion exchange capacity of 0.89 meq / g was obtained.

得られたフッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ１）を得た。該フィルム（ａ１）の断面を光学顕微鏡で観察した結果、層Ａ−２の厚みが８０μｍ、層Ｂの厚みが１３μｍであった。なお、層Ａ−２と層Ｂとは偏光をかけることによって区別した。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ１）を得た。   The obtained fluoropolymer A-2 and fluoropolymer B were co-extruded by means of an apparatus equipped with two extruders, a two-layer co-extrusion T-die, and a take-out machine. A layer film (a1) was obtained. As a result of observing the cross section of the film (a1) with an optical microscope, the thickness of the layer A-2 was 80 μm, and the thickness of the layer B was 13 μm. Layer A-2 and layer B were distinguished by applying polarized light. Moreover, the single layer film (b1) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ１）、強化芯材、２層フィルム（ａ１）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。   On the drum that has a heating source and a vacuum source inside, and has a large number of fine holes on the surface, air-permeable heat-resistant release paper, single-layer film (b1), reinforced core material, two-layer film (a1) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane.

強化芯材として、ポリテトラフルオロエチレン（ＰＴＦＥ）製１００デニールのテープヤーンに９００回／ｍの撚りをかけ糸状としたものを２４本／インチとなるよう平織りして厚み１００μｍの織布を得た。得られた織布を加熱された金属ロールで圧着し織布の厚みを７０μｍに調製した。このとき、ＰＴＦＥ糸のみの開口率は７５％であった。   As a reinforcing core material, a 100-denier tape yarn made of polytetrafluoroethylene (PTFE) was twisted 900 times / m to obtain a woven fabric having a thickness of 100 μm. . The obtained woven fabric was pressure-bonded with a heated metal roll to adjust the thickness of the woven fabric to 70 μm. At this time, the opening ratio of only the PTFE yarn was 75%.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で８０℃の温度で０．５時間加水分解し、その後、５０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて１時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 80 ° C. for 0.5 hour, and then 0.6 N (N) under the condition of 50 ° C. Salt exchange treatment was performed using NaOH solution for 1 hour.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９５であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.95. The measurement results are shown in Table 1.

［比較例１］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Comparative Example 1]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

含フッ素重合体層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比８．５：１で共重合し、イオン交換容量が０．８０ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the fluoropolymer layer B, the monomer (X 1 = F, X 2 = F) represented by the general formula (1) and the single unit represented by the general formula (3) are used. The polymer (c = 1, d = 2, Y = CF 3 , R = CH 3 ) was copolymerized at a molar ratio of 8.5: 1 to obtain a polymer having an ion exchange capacity of 0.80 meq / g. .

得られたフッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ５）を得た。該フィルムの断面を光学顕微鏡で観察した結果、層Ａ−２の厚みが８０μｍ、層Ｂの厚みが１３μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ５）を得た。   The obtained fluoropolymer A-2 and fluoropolymer B were co-extruded by means of an apparatus equipped with two extruders, a two-layer co-extrusion T-die, and a take-out machine. A layer film (a5) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of layer A-2 was 80 μm, and the thickness of layer B was 13 μm. Moreover, the single layer film (b5) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ５）、強化芯材、２層フィルム（ａ５）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材としては、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and a large number of fine holes on the surface, a gas-resistant heat-resistant release paper, a single layer film (b5), a reinforcing core material, and a two-layer film (a5) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. As the reinforcing core material, the same material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で８０℃の温度で０．５時間加水分解し、その後、５０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて１時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 80 ° C. for 0.5 hour, and then 0.6 N (N) under the condition of 50 ° C. Salt exchange treatment was performed using NaOH solution for 1 hour.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加えボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。電解は含フッ素重合体層Ａが陽極側に向けて配置された前述の電解槽で、６ｋＡ／ｍ2の電流密度で、温度を８５℃に設定して７日間行った。測定した項目は、電解電圧、電流効率、生成する苛性ソーダ中の塩化ナトリウム量であり、それぞれ、電解開始後７日目の測定値で電解性能を評価した。この時、（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９８であった。電流効率は実施例１と同様の方法により測定した。 The ion exchange membrane obtained as described above was electrolyzed. The electrolysis was carried out for 7 days at a current density of 6 kA / m 2 and a temperature of 85 ° C. in the above-described electrolytic cell in which the fluoropolymer layer A was disposed toward the anode side. The items measured were the electrolysis voltage, current efficiency, and the amount of sodium chloride in the caustic soda produced, and the electrolysis performance was evaluated based on the measured values on the seventh day after the start of electrolysis. At this time, the value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.98. The current efficiency was measured by the same method as in Example 1.

［比較例２］
含フッ素重合体Ａ−１として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Comparative Example 2]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表わされる単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

含フッ素重合体層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．５：１で共重合し、イオン交換容量が０．８９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the fluoropolymer layer B, the monomer (X 1 = F, X 2 = F) represented by the general formula (1) and the single unit represented by the general formula (3) are used. The polymer (c = 1, d = 2, Y = CF 3 , R = CH 3 ) was copolymerized at a molar ratio of 7.5: 1 to obtain a polymer having an ion exchange capacity of 0.89 meq / g. .

得られたフッ素重合体Ａ−２とフッ素重合体Ｂを、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ６）を得た。該フィルムの断面を光学顕微鏡で観察した結果、層Ａ−２の厚みが８０μｍ、層Ｂの厚みが１３μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ６）を得た。   The obtained fluoropolymer A-2 and fluoropolymer B were co-extruded by means of an apparatus equipped with two extruders, a two-layer co-extrusion T-die, and a take-out machine. A layer film (a6) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of layer A-2 was 80 μm, and the thickness of layer B was 13 μm. Further, a single layer film (b6) of layer A-1 having a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ６）、強化芯材、２層フィルム（ａ６）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材としては、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and having a large number of fine holes on the surface, air-permeable heat-resistant release paper, single-layer film (b6), reinforced core material, two-layer film (a6) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. As the reinforcing core material, the same material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で５０℃の温度で０．５時間加水分解し、その後、９５℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて５時間塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 50 ° C. for 0.5 hours, and then 0.6 N (N) under the condition of 95 ° C. Salt exchange treatment was performed using NaOH solution for 5 hours.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. A suspension in which 40% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to the solution and uniformly dispersed by a ball mill was obtained. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．７７であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.77. The measurement results are shown in Table 1.

［比較例３］
含フッ素重合体Ａ−１として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Comparative Example 3]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９８ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.98 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比８．５：１で共重合し、イオン交換容量が０．８０ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (3) (c = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 8.5: 1, a polymer having an ion exchange capacity of 0.80 meq / g was obtained.

フッ素重合体Ａ−２とフッ素重合体Ｂをし、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ５）を得た。該フィルムの断面を光学顕微鏡で観察した結果、含フッ素重合体層Ａ−２の厚みが７５μｍ、層Ｂの厚みが１５μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ５）を得た。   Fluoropolymer A-2 and Fluoropolymer B, co-extruded with two extruders, two-layer co-extrusion T-die, and a take-out machine, and a two-layer film with a thickness of 93 μm (A5) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of the fluoropolymer layer A-2 was 75 μm, and the thickness of the layer B was 15 μm. Moreover, the single layer film (b5) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ５）、強化芯材、２層フィルム（ａ５）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材は、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and a large number of fine holes on the surface, a gas-resistant heat-resistant release paper, a single layer film (b5), a reinforcing core material, and a two-layer film (a5) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. The same reinforcing core material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で７５℃の温度で０．７５時間加水分解し、その後、８５℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 75 ° C. for 0.75 hour, and then 0.6 N (N) under the condition of 85 ° C. Salt exchange treatment was performed using NaOH solution.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に平均一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. To the solution, 40% by mass of zirconium oxide having an average primary particle diameter of 1 μm was added, and a suspension was obtained by uniformly dispersing with a ball mill. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９８であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.98. The measurement results are shown in Table 1.

［比較例４］
含フッ素重合体Ａ−１として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Comparative Example 4]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９８ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.98 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比８．５：１で共重合し、イオン交換容量が０．８０ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (3) (c = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 8.5: 1, a polymer having an ion exchange capacity of 0.80 meq / g was obtained.

フッ素重合体Ａ−２とフッ素重合体Ｂをし、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み９３μｍの２層フィルム（ａ５）を得た。該フィルムの断面を光学顕微鏡で観察した結果、含フッ素重合体層Ａ−２の厚みが７５μｍ、層Ｂの厚みが１５μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ５）を得た。   Fluoropolymer A-2 and Fluoropolymer B, co-extruded with two extruders, two-layer co-extrusion T-die, and a take-out machine, and a two-layer film with a thickness of 93 μm (A5) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of the fluoropolymer layer A-2 was 75 μm, and the thickness of the layer B was 15 μm. Moreover, the single layer film (b5) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ５）、強化芯材、２層フィルム（ａ５）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材は、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and a large number of fine holes on the surface, a gas-resistant heat-resistant release paper, a single layer film (b5), a reinforcing core material, and a two-layer film (a5) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. The same reinforcing core material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で９０℃の温度で０．７５時間加水分解し、その後、８５℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) KOH at a temperature of 90 ° C. for 0.75 hour, and then 0.6 N (N) under the condition of 85 ° C. Salt exchange treatment was performed using NaOH solution.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に平均一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. To the solution, 40% by mass of zirconium oxide having an average primary particle diameter of 1 μm was added, and a suspension was obtained by uniformly dispersing with a ball mill. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９７であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.97. The measurement results are shown in Table 1.

［比較例５］
含フッ素重合体Ａ−１として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５：１で共重合し、イオン交換容量が１．０５ｍ当量／ｇのポリマーを得た。 [Comparative Example 5]
As the fluoropolymer A-1, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5: 1 to obtain a polymer having an ion exchange capacity of 1.05 meq / g.

含フッ素重合体Ａ−２として、前記一般式（１）で表される単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（２）で表される単量体（ａ＝１、ｂ＝２、Ｙ＝ＣＦ3）とをモル比５．７：１で共重合し、イオン交換容量が０．９９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer A-2, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (2) (a = 1, b = 2, Y = CF 3 ) at a molar ratio of 5.7: 1 to obtain a polymer having an ion exchange capacity of 0.99 meq / g.

層Ｂを形成する含フッ素重合体Ｂとして、前記一般式（１）で表わされる単量体（Ｘ1＝Ｆ、Ｘ2＝Ｆ）と前記一般式（３）で表わされる単量体（ｃ＝１、ｄ＝２、Ｙ＝ＣＦ3、Ｒ＝ＣＨ3）とをモル比７．５：１で共重合し、イオン交換容量が０．８９ｍ当量／ｇのポリマーを得た。 As the fluoropolymer B forming the layer B, the monomer represented by the general formula (1) (X 1 = F, X 2 = F) and the monomer represented by the general formula (3) (c = 1, d = 2, Y = CF 3 , R = CH 3 ) at a molar ratio of 7.5: 1, a polymer having an ion exchange capacity of 0.89 meq / g was obtained.

フッ素重合体Ａ−２とフッ素重合体Ｂをし、２台の押し出し機、２層用の共押し出し用Ｔダイ、及び引き取り機を備えた装置により、共押しを行い、厚み１０５μｍの２層フィルム（ａ５）を得た。該フィルムの断面を光学顕微鏡で観察した結果、含フッ素重合体層Ａ−２の厚みが８０μｍ、層Ｂの厚みが２５μｍであった。また、単層Ｔダイにて厚み２０μｍの層Ａ−１の単層フィルム（ｂ５）を得た。   Fluoropolymer A-2 and Fluoropolymer B are co-extruded by a device equipped with two extruders, two-layer co-extrusion T-die, and a take-out machine, and a two-layer film having a thickness of 105 μm (A5) was obtained. As a result of observing the cross section of the film with an optical microscope, the thickness of the fluoropolymer layer A-2 was 80 μm, and the thickness of the layer B was 25 μm. Moreover, the single layer film (b5) of the layer A-1 with a thickness of 20 μm was obtained by a single layer T die.

内部に加熱源及び真空源を有し、表面に多数の微細孔を有するドラム上に、透気性のある耐熱離型紙、単層フィルム（ｂ５）、強化芯材、２層フィルム（ａ５）を順番に積層し、２３０℃の温度及び−６５０ｍｍＨｇの減圧下で各材料間の空気を排除しながら一体化し、複合膜を得た。強化芯材は、実施例１と同様のものを用いた。   On the drum having a heating source and a vacuum source inside, and a large number of fine holes on the surface, a gas-resistant heat-resistant release paper, a single layer film (b5), a reinforcing core material, and a two-layer film (a5) in this order And was integrated while excluding air between the materials at a temperature of 230 ° C. and a reduced pressure of −650 mmHg to obtain a composite membrane. The same reinforcing core material as in Example 1 was used.

この複合膜をＤＭＳＯ３０質量％、４．０規定（Ｎ）のＫＯＨを含む水溶液中で８０℃の温度で０．５時間加水分解し、その後、５０℃の条件下、０．６規定（Ｎ）ＮａＯＨ溶液を用いて塩交換処理を行った。   This composite membrane was hydrolyzed in an aqueous solution containing 30% by mass of DMSO and 4.0 N (N) of KOH at a temperature of 80 ° C. for 0.5 hour, and then 0.6 N (N) under the condition of 50 ° C. Salt exchange treatment was performed using NaOH solution.

水とエタノールの５０／５０質量部の混合溶液に、イオン交換容量が１．０ｍ当量／ｇのＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3ＳＯ2Ｆの共重合体を加水分解してなるスルホン酸基を有するフッ素系重合体を２０質量％溶解させた。その溶液に平均一次粒子径１μｍの酸化ジルコニウム４０質量％加え、ボールミルにて均一に分散させた懸濁液を得た。この懸濁液を前記加水分解及び塩交換処理後のイオン交換膜の両面にスプレー法により塗布し乾燥させる事により、コーティング層を形成させた。 CF 2 ═CF 2 and CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 SO 2 F having an ion exchange capacity of 1.0 meq / g in a mixed solution of 50/50 parts by mass of water and ethanol 20% by mass of a fluorinated polymer having a sulfonic acid group obtained by hydrolyzing the copolymer was dissolved. To the solution, 40% by mass of zirconium oxide having an average primary particle diameter of 1 μm was added, and a suspension was obtained by uniformly dispersing with a ball mill. The suspension was applied to both surfaces of the ion exchange membrane after the hydrolysis and salt exchange treatment by a spray method and dried to form a coating layer.

上記のようにして得られたイオン交換膜について、電解を行った。（電解後の層Ｂのイオンクラスター径）／（電解前の層Ｂのイオンクラスター径）の値は０．９７であった。測定結果を表１に示す。   The ion exchange membrane obtained as described above was electrolyzed. The value of (ion cluster diameter of layer B after electrolysis) / (ion cluster diameter of layer B before electrolysis) was 0.97. The measurement results are shown in Table 1.

上記実施例及び比較例のイオン交換膜の組成及び特性等を表１に示す。   Table 1 shows the compositions and characteristics of the ion exchange membranes of the above Examples and Comparative Examples.

実施例１〜４のイオン交換膜は、電解性能が良好であり、かつ引張強度及び引張伸度の強度評価の結果も電解に十分耐え得る値を示した。
一方、比較例１のイオン交換膜は、強度評価の結果は良好であったものの電解電圧が実施例１〜４に比べて高かった。
比較例２のイオン交換膜は、強度評価の結果は良好であったものの電解電圧が大きく上昇した。
比較例３〜４のイオン交換膜は、強度評価の結果は良好であったものの電解電圧が実施例１〜４に比べて高かった。
比較例５のイオン交換膜は、強度評価の結果は良好であったものの電解電圧が実施例１〜４に比べて高かった。 The ion exchange membranes of Examples 1 to 4 had good electrolytic performance, and the results of strength evaluation of tensile strength and tensile elongation showed values that could withstand electrolysis sufficiently.
On the other hand, although the ion exchange membrane of Comparative Example 1 had good strength evaluation results, the electrolysis voltage was higher than that of Examples 1 to 4.
In the ion exchange membrane of Comparative Example 2, although the strength evaluation result was good, the electrolysis voltage increased significantly.
Although the ion exchange membranes of Comparative Examples 3 to 4 had good strength evaluation results, the electrolysis voltage was higher than that of Examples 1 to 4.
Although the ion exchange membrane of Comparative Example 5 had good strength evaluation results, the electrolysis voltage was higher than that of Examples 1 to 4.

本出願は、２０１５年５月１８日出願の日本特許出願（特願２０１５−１０１２９２号）に基づくものであり、その内容はここに参照として取り込まれる。   This application is based on a Japanese patent application filed on May 18, 2015 (Japanese Patent Application No. 2015-101292), the contents of which are incorporated herein by reference.

本発明のイオン交換膜は、塩化アルカリ電気分解の分野で、好適に利用できる。   The ion exchange membrane of the present invention can be suitably used in the field of alkali chloride electrolysis.

１ イオン交換膜
２ａ 連通孔
２ｂ 連通孔
３ 強化芯材
４ 層Ａ
５ 層Ｂ
６ コーティング層
７ コーティング層
８ 層Ａの陽極側表面に面している箇所
α 電解層の陽極側
β 電解層の陰極側
１１ 陽極
１２ 陰極
１３ 電解槽 DESCRIPTION OF SYMBOLS 1 Ion exchange membrane 2a Communication hole 2b Communication hole 3 Reinforcement core material 4 Layer A
5 layers B
6 Coating layer 7 Coating layer 8 Location facing the anode side surface of layer A α Anode side of electrolytic layer β Cathode side of electrolytic layer 11 Anode 12 Cathode 13 Electrolyzer

Claims (6)

スルホン酸基を有する含フッ素重合体を含む層Ａと、
カルボン酸基を有する含フッ素重合体を含む層Ｂと、
を有し、
下記電解条件における電解前の前記層Ｂのイオンクラスター径に対する、前記電解後の前記層Ｂのイオンクラスター径の割合〔（前記電解後の層Ｂのイオンクラスター径）／（前記電解前の層Ｂのイオンクラスター径）〕が０．８３〜０．９５である、イオン交換膜であって、
前記層Ａは、下記式（２）で表される化合物の加水分解由来のスルホン酸基を有する重合体を含み、
前記層Ｂは、下記式（３）で表される化合物の加水分解由来のカルボン酸基を有する重合体を含む、イオン交換膜：
（電解条件）
３．５規定（Ｎ）の塩化ナトリウム水溶液が供給された陽極室と、１０．８規定（Ｎ）の水酸化ナトリウム水溶液が供給された陰極室との間に前記イオン交換膜が配置されたゼロギャップ電解槽において、温度が８５℃、電流密度が６ｋＡ／ｍ2の条件で７日間電解を行う。
ＣＦ 2 ＝ＣＦ−（ＯＣＦ 2 ＣＹＦ） a −Ｏ−（ＣＦ 2 ） b −ＳＯ 2 Ｆ （２）
（式（２）中、ａは０〜２の整数、ｂは１〜４の整数、Ｙは−Ｆ又は−ＣＦ 3 を表す。）
ＣＦ 2 ＝ＣＦ−（ＯＣＦ 2 ＣＹＦ） c −Ｏ−（ＣＦ 2 ） d −ＣＯＯＲ （３）
（式（３）中、ｃは０〜２の整数、ｄは１〜４の整数、Ｙは−Ｆ又は−ＣＦ 3 、Ｒは−ＣＨ 3 、−Ｃ 2 Ｈ 5 、又は−Ｃ 3 Ｈ 7 を表す。） A layer A containing a fluoropolymer having a sulfonic acid group;
A layer B containing a fluoropolymer having a carboxylic acid group;
Have
Ratio of ion cluster diameter of layer B after electrolysis to the ion cluster diameter of layer B before electrolysis under the following electrolysis conditions [(ion cluster diameter of layer B after electrolysis) / (layer B before electrolysis] The ion cluster diameter))] is 0.83 to 0.95 ,
The layer A includes a polymer having a sulfonic acid group derived from hydrolysis of a compound represented by the following formula (2),
The layer B includes an ion exchange membrane containing a polymer having a carboxylic acid group derived from hydrolysis of a compound represented by the following formula (3) :
(Electrolytic conditions)
Zero in which the ion exchange membrane is disposed between an anode chamber supplied with a 3.5 N (N) sodium chloride aqueous solution and a cathode chamber supplied with a 10.8 N (N) sodium hydroxide aqueous solution In the gap electrolytic cell, electrolysis is performed for 7 days under the conditions of a temperature of 85 ° C. and a current density of 6 kA / m 2 .
CF 2 = CF- (OCF 2 CYF ) a -O- (CF 2) b -SO 2 F (2)
(In Formula (2), a represents an integer of 0 to 2, b represents an integer of 1 to 4, and Y represents —F or —CF 3. )
CF 2 = CF- (OCF 2 CYF ) c -O- (CF 2) d -COOR (3)
(In the formula (3), c is an integer of 0 to 2, d is an integer from 1 to 4, Y is -F or -CF 3, R is -CH 3, -C 2 H 5, or -C 3 H 7 Represents.) 前記電解前の層Ｂのイオンクラスター径が２．５〜４．０ｎｍであり、
前記電解後の層Ｂのイオンクラスター径が２．０〜３．３ｎｍである、請求項１に記載のイオン交換膜。 The ion cluster diameter of the layer B before electrolysis is 2.5 to 4.0 nm,
The ion exchange membrane according to claim 1, wherein the ion cluster diameter of the layer B after electrolysis is 2.0 to 3.3 nm. 前記電解前における、前記層Ａの厚みと前記層Ｂの厚みとの合計が５５μｍ以上である、請求項１又は２に記載のイオン交換膜。   The ion exchange membrane according to claim 1 or 2, wherein the total of the thickness of the layer A and the thickness of the layer B before the electrolysis is 55 µm or more. 前記電解前の層Ａのイオンクラスター径が３．０〜４．５ｎｍである、請求項１〜３のいずれか１項に記載のイオン交換膜。   The ion exchange membrane according to any one of claims 1 to 3, wherein an ion cluster diameter of the layer A before electrolysis is 3.0 to 4.5 nm. 前記電解前の層Ａの厚さが５０〜１８０μｍであり、
前記電解前の層Ｂの厚さが５〜２０μｍである、請求項１〜４のいずれか１項に記載のイオン交換膜。 The thickness of the layer A before electrolysis is 50 to 180 μm,
The ion exchange membrane of any one of Claims 1-4 whose thickness of the layer B before the said electrolysis is 5-20 micrometers. 請求項１〜５のいずれか１項に記載のイオン交換膜を備える、電解槽。
An electrolytic cell comprising the ion exchange membrane according to any one of claims 1 to 5 .
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